Giovanna Barbarella

Organic single-layer white light-emitting diodes by exciplex emission from spin-coated blends of blue-emitting molecules

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.

Multifunctional Nanostructures Based on Inorganic Nanoparticles and Oligothiophenes and Their Exploitation for Cellular Studies

The combination of materials that possess different properties (such as, for instance, fluorescence and magnetism) into one single object of nanoscale size represents an attractive challenge for biotechnology, especially for their potential relevance in biomedical applications. We report here the preparation of novel bifunctional conjugates based on the linkage of inorganic nanoparticles to organic oligothiophene fluorophores (OTFs). In comparison to the organic dyes commonly used in bioimaging and more similarly to colloidal quantum dots, OTFs have broad optical absorption spectra, and therefore OTF fluorophores emitting at different colors can be excited with a single excitation source, allowing for easier multiplexing analysis. In this work we show the preparation of OTF-nanoparticle conjugates based on gold and iron oxide nanoparticles and their characterization using different techniques such as gel electrophoresis, photoluminescence spectroscopy, dynamic light scattering, and so on. In addition, by performing an in vitro study on human tumor cells we show that OTF-nanoparticle conjugates emitting at different colors can be used for multiplexing detection. Also, in the case of iron oxide-OTF conjugates, once uptaken by the cells, we show that they preserve both their fluorescent and their magnetic properties.

High-efficiency oligothiopene-based light-emitting diodes

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.

Amplified spontaneous emission and efficient tunable laser emission from a substituted thiophene-based oligomer

We investigated gain and lasing in spin-coated films of a soluble substituted oligothiophene. With increasing excitation power, the photoluminescence spectra show a clear line narrowing due to amplified spontaneous emission. We measure a low threshold (20 μJ cm−2) for line narrowing and a large gain cross section (6×10−16 cm2), indicating that this molecule is a promising active material for organic solid-state lasers. As a demonstrator, we realize a transverse electromagnetic (TEM00) single-mode laser with tunable emission from the yellow to the red (a range of 37 nm), with a pump threshold as low as 18 μJ cm−2 and efficiency of 1.9%. These results are among the best so far reported for organic lasers.

Oligomer-based organic distributed feedback lasers by room-temperature nanoimprint lithography

Room-temperature nanoimprint lithography in air is used in order to pattern a nonthermoplastic, low-molar-mass thiophene-based pentamer with excellent gain properties. No degradation of the luminescence efficiency of the active medium was observed after patterning. In this way, we fabricated single-mode emission distributed feedback lasers having a threshold excitation fluence of 140 μJ/cm2. The lasing line is peaked at 637 nm and exhibits a linewidth of less than 0.7 nm and a well-behaved input-output characteristic in the whole range of pump fluences. These results demonstrate room-temperature nanoimprint lithography as powerful and straightforward fabrication technique for oligomer-based nanostructured optoelectronic devices.

Polymer-based electrochromic devices—I. Poly(3-methylthiophenes)

Abstract The basic aspects of electrochromism induced by a p-doping/undoping process of conjugated polymers are briefly described. The most important requisites for an electrochromic device are discussed, and polymer electrochromic performance data as well as the test results of a polymer-based variable light transmission electrochromic device are reported. The colour contrast control of conjugated polymers by “tailoring” their conjugation length is discussed and spectroelectrochemical data of poly(3-methylthiophenes) electrosynthesized from 3-methylthiophene isomeric dimers and isomeric tetramers are reported.

Magnetic-Fluorescent Colloidal Nanobeads: Preparation and Exploitation in Cell Separation Experiments

Nanostructures displaying fluorescence and magnetic properties at the same time are potentially useful for achieving simultaneous bio-separation and bio-sensing (e.g., magnetic separation coupled with multiplexing optical detection of different tumour cell populations). Spherical nanobeads that display both fluorescent and magnetic features are reported; they are fabricated by grafting fluorescent oligothiophene molecules to an amphiphilic polymer that is then used to enwrap iron oxide nanoparticles, which acts as the magnetic domain. By tuning experimental conditions, control over the number of magnetic nanoparticles per bead and over the bead diameter (30-400 nm) was achieved. A cell separation efficiency of the level required for cell sorting applications is also reported.

Microwave-assisted synthesis of thiophene fluorophores, labeling and multilabeling of monoclonal antibodies, and long lasting staining of fixed cells.

We report the expedient microwave-assisted synthesis of thiophene based 4-sulfo-2,3,5,6,-tetrafluorophenyl esters whose molecular structure was engineered to achieve blue to red bright fluorescence. The reactivity toward monoclonal antibodies of the newly synthesized fluorophores was analyzed in comparison with that of the corresponding N-succinimidyl esters. Single-fluorophore and multiple-fluorophore labeled antibodies were easily prepared with both types of esters. Multiple-fluorophore labeling with blue and orange emitting fluorophores resulted in white fluorescent antibodies. Thiophene based fluorophores displayed unprecedented fluorescence stability in immunostaining experiments. First-principles TD-DFT theoretical calculations helped us to interpret the behavior of fluorescence emission in different environments.

Live-Cell-Permeant Thiophene Fluorophores and Cell-Mediated Formation of Fluorescent Fibrils

In our search for thiophene fluorophores that can overcome the limits of currently available organic dyes in live-cell staining, we synthesized biocompatible dithienothiophene-S,S-dioxide derivatives (DTTOs) that were spontaneously taken up by live mouse embryonic fibroblasts and HeLa cells. Upon treatment with DTTOs, the cells secreted nanostructured fluorescent fibrils, while cell viability remained unaltered. Comparison with the behavior of other cell-permeant, newly synthesized thiophene fluorophores showed that the formation of fluorescent fibrils was peculiar to DTTO dyes. Laser scanning confocal microscopy of the fluorescent fibrils showed that most of them were characterized by helical supramolecular organization. Electrophoretic analysis and theoretical calculations suggested that the DTTOs were selectively recognized by the HyPro component of procollagen polypeptide chains and incorporated through the formation of multiple H-bondings.

Microwave-assisted synthesis of oligothiophene semiconductors in aqueous media using silica and chitosan supported Pd catalysts

We report an innovative heterogeneous procedure for the preparation of highly pure thiophene oligomers via microwave-assisted Pd catalysis by using silica- and chitosan-supported Pd complexes. This approach is very efficient and greener than the existing homogeneous methodology as it combines a very efficient reaction with improved catalyst separation. Our new, efficient and cleaner microwave approach smoothly afforded the preparation of coupled products in high yields (up to 87% isolated yield, 30–100 min). Thienyl iodides or activated bromides were employed as starting materials and KF as base. The microwave reaction was carried out in aqueous ethanol. The heterogeneous catalyst can be easily removed from the reaction mixture by filtration and reused in consecutive reactions (up to 4 times).