Pseudomorphic Transformation in Nanostructured Thiophene-Based Materials.

This study reveals the capability of nanostructured organic materials to undergo pseudomorphic transformations, a ubiquitous phenomenon occurring in the mineral kingdom that involves the replacement of a mineral phase with a new one while retaining the original shape and volume. Specifically, it is demonstrated that the postoxidation process induced by HOF·CHCN on preformed thiophene-based 1D nanostructures preserves their macro/microscopic morphology while remarkably altering their electro-optical properties by forming a new oxygenated phase. Experimental evidence proves that this transformation proceeds via an interface-coupled dissolution-precipitation mechanism, leading to the growth of a porous oxidized shell that varies in thickness with exposure time, enveloping the pristine smooth core.

Phage-Templated Synthesis of Targeted Photoactive 1D-Thiophene Nanoparticles.

Thiophene-based nanoparticles (TNPs) are promising therapeutic and imaging agents. Here, using an innovative phage-templated synthesis, a strategy able to bypass the current limitations of TNPs in nanomedicine applications is proposed. The phage capsid is decorated with oligothiophene derivatives, transforming the virus in a 1D-thiophene nanoparticle (1D-TNP).

Multifunctional Photoelectroactive Materials for Optoelectronic Applications Based on Thieno[3,4-b]pyrazines and Thieno[1,2,5]thiadiazoles.

In this study, we introduce a novel family of symmetrical thiophene-based small molecules with a Donor-Acceptor-Donor structure. These compounds feature three different acceptor units: benzo[c][1,2,5]thiadiazole (Bz), thieno[3,4-b]pyrazine (Pz), and thieno[1,2,5]thiadiazole (Tz), coupled with electron donor units based on a carbazole-thiophene derivative. Using Density Functional Theory (DFT), we investigate how the molecular geometry and strength of the central acceptor unit impact the redox and spectroscopic properties.

Core-Shell Architecture in Poly(3-hexylthiophene) Nanoparticles: Tuning of the Photophysical Properties for Enhanced Neuronal Photostimulation.

This study shows that entirely thiophene-based core@shell nanoparticles, in which the shell is made of the oxidized form of the core polymer (P3HT@PTDO NPs), result in a type II interface at the particle surface. This enables the development of advanced photon nanotransducers with unique chemical-physical and biofunctional properties due to the core@shell nanoarchitecture. We demonstrate that P3HT@PTDO NPs present a different spatial localization of the excitation energy with respect to the nonoxidized NPs, showing a prevalence of surface states as a result of a different alignment of the HOMO/LUMO energy levels between the core and shell.

Spontaneous Coassembly of the Protein Terthiophene into Fluorescent Electroactive Microfibers in 2D and 3D Cell Cultures.

Protein-based microfibers are biomaterials of paramount importance in materials science, nanotechnology, and medicine. Here we describe the spontaneous in situ formation and secretion of nanostructured protein microfibers in 2D and 3D cell cultures of 3T3 fibroblasts and B104 neuroblastoma cells upon treatment with a micromolar solution of either unmodified terthiophene or terthiophene modified by mono-oxygenation (thiophene → thiophene -oxide) or dioxygenation (thiophene → thiophene ,-dioxide) of the inner ring. We demonstrate via metabolic cytotoxicity tests that modification to the -oxide leads to a severe drop in cell viability.

Human Serum Albumin-Oligothiophene Bioconjugate: A Phototheranostic Platform for Localized Killing of Cancer Cells by Precise Light Activation.

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.

Sterilization of Semiconductive Nanomaterials: The Case of Water-Suspended Poly-3-Hexylthiophene Nanoparticles.

In this work, the feasibility of sterilizing a water suspension of poly-3-hexylthiophene nanoparticles (P3HT-NPs) is investigated using ionizing radiation, either γ-rays or high-energy electrons (e-beam). It is found that regardless of the irradiation source, the size, polydispersity, aggregation stability, and morphology of the NPs are not affected by the treatment. Furthermore, the impact of ionizing radiation on the physicochemical properties of NPs at different absorbed radiation doses (10-25 kGy) and dose rates (kGy time ) is evaluated through different spectroscopic techniques.

In Vivo Bioengineering of Fluorescent Conductive Protein-Dye Microfibers.

Engineering protein-based biomaterials is extremely challenging in bioelectronics, medicine, and materials science, as mechanical, electrical, and optical properties need to be merged to biocompatibility and resistance to biodegradation. An effective strategy is the engineering of physiological processes in situ, by addition of new properties to endogenous components. Here we show that a green fluorescent semiconducting thiophene dye, DTTO, promotes, in vivo, the biogenesis of fluorescent conductive protein microfibers via metabolic pathways.

Nanostructuring Iridium Complexes into Crystalline Phosphorescent Nanoparticles: Structural Characterization, Photophysics, and Biological Applications.

One of the key challenges in materials science is to control the properties of a material by directing its supramolecular arrangement. Here we show that iridium complexes, such as FIrpic, Ir-PPY, and Ir-MDQ, can be organized into crystalline and phosphorescent nanoparticles through the nanoprecipitation method, which allows thorough modification of their functional properties. Moreover, we found that it is possible to combine different iridium complexes into a single multicomponent nanostructure, thus creating nanoparticles whose photonic properties derive from the close spatial proximity of the electronic excited states of the different Ir complexes.

Enantiopure polythiophene nanoparticles. Chirality dependence of cellular uptake, intracellular distribution and antimicrobial activity.

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 or chiral carbon is reported. Enantiopure chiral nanoparticles ( or NPs) were prepared from the polymers by a reprecipitation method.

Thermodynamically versus Kinetically Controlled Self-Assembly of a Naphthalenediimide-Thiophene Derivative: From Crystalline, Fluorescent, n-Type Semiconducting 1D Needles to Nanofibers.

The control over aggregation pathways is a key requirement for present and future technologies, as it can provide access to a variety of sophisticated structures with unique functional properties. In this work, we demonstrate an unprecedented control over the supramolecular self-assembly of a semiconductive material, based on a naphthalenediimide core functionalized with phenyl-thiophene moieties at the imide termini, by trapping the molecules into different arrangements depending on the crystallization conditions. The control of the solvent evaporation rate enables the growth of highly elaborated hierarchical self-assembled structures: either in an energy-minimum thermodynamic state when the solvent is slowly evaporated forming needle-shaped crystals (polymorph α) or in a local energy-minimum state when the solvent is rapidly evaporated leading to the formation of nanofibers (polymorph β).

One- and two-photon absorption properties of quadrupolar thiophene-based dyes with acceptors of varying strengths.

The one-photon (1P) and two-photon (2P) absorption properties of three quadrupolar dyes, featuring thiophene as a donor and acceptors of varying strengths, are determined by a combination of experimental and computational methods employing the density functional theory (DFT). The emission shifts in different solvents are well reproduced by time-dependent DFT calculations with the linear response and state specific approaches in the framework of the polarizable continuum model. The calculations show that the energies of both 1P- and 2P-active states decrease with an increase of the strength of the acceptor.

Photocatalytic Activity of Polymer Nanoparticles Modulates Intracellular Calcium Dynamics and Reactive Oxygen Species in HEK-293 Cells.

Optical modulation of living cells activity by light-absorbing exogenous materials is gaining increasing interest, due to the possibility both to achieve high spatial and temporal resolution with a minimally invasive and reversible technique and to avoid the need of viral transfection with light-sensitive proteins. In this context, conjugated polymers represent ideal candidates for photo-transduction, due to their excellent optoelectronic and biocompatibility properties. In this work, we demonstrate that organic polymer nanoparticles, based on poly(3-hexylthiophene) conjugated polymer, establish a functional interaction with an cell model (Human Embryonic Kidney cells, HEK-293).

The lost ability to distinguish between self and other voice following a brain lesion.

Mechanisms underlying the self/other distinction have been mainly investigated focusing on visual, tactile or proprioceptive cues, whereas very little is known about the contribution of acoustical information. Here the ability to distinguish between self and others' voice is investigated by using a neuropsychological approach. Right (RBD) and left brain damaged (LBD) patients and healthy controls were submitted to a voice discrimination and a voice recognition task.

Engineering thiophene-based nanoparticles to induce phototransduction in live cells under illumination.

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 H NMR of nanoparticles prepared using THF-d8/DO (solvent/non-solvent) we demonstrate that the hydrolysis of the N-succinimidyl-ester group to free N-hydroxysuccinimide takes place slowly over several hours.

Semiconducting polymers are light nanotransducers in eyeless animals.

Current implant technology uses electrical signals at the electrode-neural interface. This rather invasive approach presents important issues in terms of performance, tolerability, and overall safety of the implants. Inducing light sensitivity in living organisms is an alternative method that provides groundbreaking opportunities in neuroscience.

Observation of J/ψϕ Structures Consistent with Exotic States from Amplitude Analysis of B^{+}→J/ψϕK^{+} Decays.

The first full amplitude analysis of B^{+}→J/ψϕK^{+} with J/ψ→μ^{+}μ^{-}, ϕ→K^{+}K^{-} decays is performed with a data sample of 3  fb^{-1} of pp collision data collected at sqrt[s]=7 and 8 TeV with the LHCb detector. The data cannot be described by a model that contains only excited kaon states decaying into ϕK^{+}, and four J/ψϕ structures are observed, each with significance over 5 standard deviations. The quantum numbers of these structures are determined with significance of at least 4 standard deviations.

Poly(3-hexylthiophene) nanoparticles for biophotonics: study of the mutual interaction with living cells.

We report on the mutual interaction between poly(3-hexylthiophene) nanoparticles (P3HT-NPs) and human embryonic kidney (HEK-293) cells. P3HT-NPs, prepared in sterile conditions and efficiently uptaken within the live cells cytosol, show well-ordered morphology, high colloidal stability and excellent biocompatibility. Electrophysiology and calcium imaging experiments demonstrate that physiological functions of live cells are fully preserved in the presence of P3HT-NPs.

Evidence for Exotic Hadron Contributions to Λ_{b}^{0}→J/ψpπ^{-} Decays.

A full amplitude analysis of Λ_{b}^{0}→J/ψpπ^{-} decays is performed with a data sample acquired with the LHCb detector from 7 and 8 TeV pp collisions, corresponding to an integrated luminosity of 3  fb^{-1}. A significantly better description of the data is achieved when, in addition to the previously observed nucleon excitations N→pπ^{-}, either the P_{c}(4380)^{+} and P_{c}(4450)^{+}→J/ψp states, previously observed in Λ_{b}^{0}→J/ψpK^{-} decays, or the Z_{c}(4200)^{-}→J/ψπ^{-} state, previously reported in B^{0}→J/ψK^{+}π^{-} decays, or all three, are included in the amplitude models. The data support a model containing all three exotic states, with a significance of more than three standard deviations.

Model-Independent Evidence for J/ψp Contributions to Λ_{b}^{0}→J/ψpK^{-} Decays.

The data sample of Λ_{b}^{0}→J/ψpK^{-} decays acquired with the LHCb detector from 7 and 8 TeV pp collisions, corresponding to an integrated luminosity of 3  fb^{-1}, is inspected for the presence of J/ψp or J/ψK^{-} contributions with minimal assumptions about K^{-}p contributions. It is demonstrated at more than nine standard deviations that Λ_{b}^{0}→J/ψpK^{-} decays cannot be described with K^{-}p contributions alone, and that J/ψp contributions play a dominant role in this incompatibility. These model-independent results support the previously obtained model-dependent evidence for P_{c}^{+}→J/ψp charmonium-pentaquark states in the same data sample.

Measurement of the CP Asymmetry in B_{s}^{0}-B[over ¯]_{s}^{0} Mixing.

The CP asymmetry in the mixing of B_{s}^{0} and B[over ¯]_{s}^{0} mesons is measured in proton-proton collision data corresponding to an integrated luminosity of 3.0  fb^{-1}, recorded by the LHCb experiment at center-of-mass energies of 7 and 8 TeV. Semileptonic B_{s}^{0} and B[over ¯]_{s}^{0} decays are studied in the inclusive mode D_{s}^{∓}μ^{±}ν[over (-)]_{μ}X with the D_{s}^{∓} mesons reconstructed in the K^{+}K^{-}π^{∓} final state.

First Observation of D^{0}-D[over ¯]^{0} Oscillations in D^{0}→K^{+}π^{-}π^{+}π^{-} Decays and Measurement of the Associated Coherence Parameters.

Charm meson oscillations are observed in a time-dependent analysis of the ratio of D^{0}→K^{+}π^{-}π^{+}π^{-} to D^{0}→K^{-}π^{+}π^{-}π^{+} decay rates, using data corresponding to an integrated luminosity of 3.0  fb^{-1} recorded by the LHCb experiment. The measurements presented are sensitive to the phase-space averaged ratio of doubly Cabibbo-suppressed to Cabibbo-favored amplitudes r_{D}^{K3π} and the product of the coherence factor R_{D}^{K3π} and a charm mixing parameter y_{K3π}^{'}.