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The development of semiconductor polymers for electronic applications requires tailored synthetic strategies to obtain materials with tunable electronic properties and morphology to enhance their properties. Towards this goal, here is reported the expedient synthesis of a novel class of thiophene-based electrochromic polymers, processable in organic solvents and as nanoparticles (NPs) in water. Their characterization and application in flexible solid-state electrochromic devices (ECDs) are described. All polymers have a repeat unit made of the same linear thienyl–phenyl–thienyl–thienyl fragment. The tuning of the electro-optical properties is achieved by introducing alkyl or alkoxy substituents in thiophene and/or by the presence of either -CH-CH- or -CH2-CH2- linkers connecting the repeat units and acting as conjugation modulators. The ECDs display a bright yellow or red/magenta color in the neutral state and dark blue in the oxidized state. Redox potentials, color contrast, switching time, and stability of the devices are reported, and it is demonstrated that the use of NPs films spray-coated from water instead of cast films from chloroform significantly improves their performance. Density functional theory calculations allow to elucidate the relationship between polymer structure and electrochromic properties and shed light on electronic structure changes upon oxidation, in agreement with spectroelectrochemistry.

The electronic, optical, and redox properties of thiophene-based materials have made them pivotal in nanoscience and nanotechnology. However, the exploitation of oligothiophenes in photodynamic therapy is hindered by their intrinsic hydrophobicity that lowers their biocompatibility and availability in water environments. Here, we developed human serum albumin (HSA)–oligothiophene bioconjugates that afford the use of insoluble oligothiophenes in physiological environments. UV–vis and electrophoresis proved the conjugation of the oligothiophene sensitizers to the protein. The bioconjugate is water-soluble and biocompatible, does not have any “dark toxicity”, and preserves HSA in the physiological monomeric form, as confirmed by dynamic light scattering and circular dichroism measurements. In contrast, upon irradiation with ultralow light doses, the bioconjugate efficiently produces reactive oxygen species (ROS) and leads to the complete eradication of cancer cells. Real-time monitoring of the photokilling activity of the HSA–oligothiophene bioconjugate shows that living cells “explode” upon irradiation. Photodependent and dose-dependent apoptosis is one of the primary mechanisms of cell death activated by bioconjugate irradiation. The bioconjugate is a novel theranostic platform able to generate ROS intracellularly and provide imaging through the fluorescence of the oligothiophene. It is also a real-time self-reporting system able to monitor the apoptotic process. The induced phototoxicity is strongly confined to the irradiated region, showing localized killing of cancer cells by precise light activation of the bioconjugate.

We report that nanoparticles prepared from appropriately functionalized polythiophenes once administered to live cells can acquire phototransduction properties under illumination, becoming photoactive sites able to absorb visible light and convert it to an electrical signal through cell membrane polarization. Amine-reactive fluorescent nanoparticles with pendant N-succinimidyl-ester groups (NPs-NHS) are prepared from polythiophenes alternating unsubstituted and 3-(2,5-dioxopyrrolidin-1-yl-8-octanoate)-substituted thiophenes by a nanoprecipitation method. By 1H NMR of nanoparticles prepared using THF-d8/D2O (solvent/non-solvent) we demonstrate that the hydrolysis of the N-succinimidyl-ester group to free N-hydroxysuccinimide takes place slowly over several hours. NPs-NHS reactivity towards primary amine groups is tested towards the NH2 of d- and l-enantiomers of tryptophan. We show that the formation of a tryptophan-nanoparticle amidic bond creates a chiral shell displaying opposite CD signals for the nanoparticles bound to d or l enantiomers. The interaction of NPs-NHS with live HEK-293 cells is monitored via LSCM. We show that the NPs-NHS are not internalized but remain docked on the cell membrane. We assume that this is mainly the result of the reaction of the NHS groups in the external layer with NH2 groups present in cell membrane proteins, although the contribution of alternative mechanisms cannot be excluded. To support this assumption LSCM experiments show that nanoparticles of comparable size obtained from poly(3-hexylthiophene), NPs-P3HT, are rapidly internalized by live HEK-293 cells. Finally, using the whole-cell current clamp technique under light illumination we demonstrate that NPs-NHS can polarize the cell membrane upon light irradiation while NPs-P3HT cannot.

Thiophene-based compounds have acquired increasing importance in materials science and technology, owing to their multiple functional properties, chemical robustness, and versatility. Research studies involving thiophene-based materials are highly interdisciplinary and range from organic electronics, in which the semiconducting properties of these materials are exploited in devices such as thin film field-effect transistors and solar cells, to bioimaging, in which their optical properties are exploited to monitor biological events involving proteins and DNA. Since all fields are concerned with the synthesis of new molecular structures, this chapter also deals with the most recent advances in the synthesis of oligo- and polythiophenes.

In recent studies it was demonstrated that temperature-dependent optical spectroscopy is a valuable tool for revealing the differences in the geometries of flexible molecules like oligothiophenes (OTs) in the ground (S0) and first excited (S1) electronic states, by examining the symmetry relations between the absorption and emission spectra: while at low temperature the spectra show mirror symmetry, pointing to planar geometries in S0 and S1, the symmetry relation breaks down at ambient temperature due to thermal population of torsional modes. In the present joint spectroscopic and theoretical study, we demonstrate that this behavior is also observed for di- and tetramethyl-substituted OTs, suggesting an essentially planar equilibrium geometry not only in S1 but also in S0, despite the increasing sterical hindrance which is imposed by the substituents. This rather surprising result is rationalized by the softness of the carbon-sulfur bond, which is able to adapt to the geometrical constraints. © the Owner Societies.

The synthesis of multicolor fluorescent oligothiophene-N-succinimidyl esters (TSEs) is reported and their optical properties are discussed with the aid of ab initio calculations. The esters were coupled to proteins and to 3’-amino-modified oligonucleotides in mild conditions and with similar modalities. A comparative study of the bioconjugate of IgG1 anti-CD3 antibody labeled with a blue fluorescent TSE and with fluorescein isothiocyanate (FITC) is reported showing that the former achieves higher photoluminescence intensity and optical stability than the latter. Fluorescence resonance energy transfer experiments with TSE labeled oligonucleotides and examples of cellular imaging via TSE labeled proteins are reported.

A structurally correlated series of cell-permeant thiophene fluorophores, characterized by intense green or red fluorescence inside live mouse embryonic fibroblasts, was developed. The fluorophores displayed rapid internalization, excellent retention inside the cells, and high optical stability in the cytosolic environment and did not alter cell viability and reproducibility. Depending on the molecular structure, they experienced distinct fate inside the cells: from bright and lasting staining of the cytoplasm to selective tagging of a small set of globular proteins. This journal is © The Royal Society of Chemistry 2014.

We investigated the uptake and release of labeled antibodies from pH-sensitive hydrogel microparticles (i.e. microgels) by means of fluorescence analysis of labeled biological samples. The poly(methacrylic acid) (PMAA) hydrogel is a carbon-based network having carboxylic groups on the surface that dissociate according to their acid-base equilibrium. The ability of the PMAA microgel to encapsulate and release anti-CD4 and anti-CD8 monoclonal antibodies (MAbs), differing for the isotype and labeled with highly photostable fluorophore, was studied in solution by photoluminescence spectroscopy. The experimental results indicated that the uptake and release of the tested antibodies were controlled by pH. Furthermore, confocal microscopy analysis in the solid state revealed that the distribution of the labeled antibodies either on the surface or in the core of the microgel matrix was related to the specific properties of these MAbs. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

We report investigations of the photoluminescence (PL) and electroluminescence (EL) of a thiophene oligomer for which we have devised a variety of substitutions aimed at enhancing the solid-state efficiency. We find that the absolute PL quantum efficiency in the solid state is up 37% for both powders or spin-coated thin films of the compound. The material thus becomes competitive for applications in organic light-emitting diodes (LEDs). EL efficiencies up to 1.2 cd/A are demonstrated in LEDs prepared with indium–tin–oxide and Ca–Al electrodes.

We report a theoretical study on the optical properties of bithiophene and terthiophene N-succinimidyl esters, which have been functionalized with a methylsulfanyl group in the alpha or the beta positions. Time-dependent density functional theory (TD-DFT) and approximate coupled-cluster singles and doubles with the resolution of identity technique (RI-CC2) calculations have been performed in the ground and excited states. The RI-CC2 results for absorption and fluorescence energies are in better qualitative agreement with experiments, whereas TD-DFT does not correctly describe the higher energy part of the absorption spectra of beta-substituted bithiophenes, due to the presence of charge-transfer states. Systems functionalized at the alpha position show a large red-shift of the main absorption and fluorescence band and a larger Stokes-shift compared to the unsubstituted species. These effects are in most cases less pronounced for the beta-substituted structures. In particular, we found that the Stokes-shift of the alpha-substituted structures is larger than the one of the beta-substituted species due to a more planar orientation of the methylsulfanyl group with respect to the neighbouring thiophene in the excited state.

The synthesis, optical characterization and redox potentials of a branched polythiophene (V-PT), obtained by the Stille polycondensation of V-shaped 2,3-dibromo-benzo[b]thiophene-1,1-dioxide and 3,3-dimethyl-5,5'-tributylstannyl-2,2'-bithiophene, are reported. The branched shape favours the suppression of aggregation effects and the presence of the benzo[b]thiophene-1,1-dioxide moiety leads to a marked increase in electron affinity. A single layer light-emitting diode having V-PT as the active material showed a luminance of 948 cd m(-2). (C) 2007 Elsevier Ltd. All rights reserved.

We report on oligothiophene N-succinimidyl esters as efficient and optically very stable fluorophores under prolonged irradiation, used as markers of monoclonal antibodies and oligonucleotides. (c) 2006 Elsevier B.V. All rights reserved.

The synthesis of the title compound ( 4 ), starting from commercial 3-bromo-4-methylthiophene, is described. The single crystal packing mode of 4 , as well as the absorption and photoluminescence properties in solution and in the solid state are reported and analyzed in relation to those of the isomeric 3,5-dimethyl-dithieno[3,2-b:2′,3′-d]thiophene-4,4-dioxide ( 7 ). The different reactivities of 4 and 7 towards bromination are analyzed in the light of the results of ab initio B3LYP/6-31G∗ calculations on both compounds.

We show how colour tunability (including white) can be achieved by controlling non-radiative intermolecular energy transfer from the donor to the acceptor in binary blends of oligomeric compounds. Blends of different concentrations of a novel functionalized thiophene-based oligomer and a low-molar-mass diamine derivative (N, N'-diphenyl-N, N'-bis(3-methylphenyl)-1,1'-biphenyl-4.4'diamine) are used to tune both the photoluminescence and the electroluminescence (EL) from red to blue, including balanced white, according to the standards of the Commission Internationale de l'Eclairage. The single-active-layer light-emitting devices, realized by spin-coating, exhibit good EL performance. In particular, the white-emitting device shows an EL efficiency of 5 x 10(-1) cd A(-1) and a luminance of more than 180 cd m(-2).

We report on white electroluminescence (EL) emission from a single-layer light-emitting diode based on a binary blend of organic soluble blue-emitting molecules, i.e., a diamine derivative and a substituted thiophene-1,1-dioxide. Weakly voltage-dependent white color, of coordinates (0.39, 0.40) according to the standard of the Commission Internationale de l’Eclairage, is obtained from the superposition of the blue emission from the donor and a low-energy peak due to a charge-transfer complex between the two molecules (exciplex). The EL spectrum is broader and more structured than the photoluminescence one: this could be due to the activation of exciplexes with different conformations as inferred from quantum-chemistry calculations.

Several films with different thickness of both beta -methyl sexithiophene and unsubstituted sexithiophene were grown on fused silica by organic molecular beam deposition in ultra-high vacuum conditions and their optical absorption properties were investigated. Because of the different molecular arrangement of the two materials, different optical spectra are observed. By comparing the absorbance spectra of samples of different thickness, the absorption coefficients of both beta -methyl sexithiophene films and sexithiophene films were deduced.

The optical properties of thin films of two different quaterthiophenes, unsubstituted and substituted, deposited on different substrates by organic molecular beam deposition are briefly illustrated. The absorption spectra of the samples present both the molecular exciton peak, characteristic of strongly interacting molecules and polarized along a preferential direction in the most ordered films, and small bands coming from less interacting or misaligned molecules; these are mostly responsible for the photoluminescence spectra.

The use of intrinsic chiral molecules opens the door to bio-imaging specific tools and to the development of target-therapy. In this work the synthesis and characterization of polythiophenes with alkyl side chains containing one R or S chiral carbon is reported. Enantiopure chiral nanoparticles (R or S NPs) were prepared from the polymers by a reprecipitation method. UV-vis, photoluminescence and circular dichroism spectroscopy of the NPs are described. In vitro analysis and metabolic assays show that both R and S NPs are efficiently taken-up by fibroblast cells without signs of toxicity. SDS-PAGE experiments show that formation of hard protein ‘corona’ enhances the chirality difference between nanoparticles. Co-localization experiments demonstrate that the cells are able to discriminate between the enantiomeric R and S nanoparticles. Finally, experiments carried out on Gram negative and Gram positive bacteria show that the enantiomeric NPs display different antibacterial activity.