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We examined the efficacy of selective inhibition of cyclin-dependent kinase 5 (CDK5) in glioblastoma by TP5. We analyzed its impact in vitro on CDK5 expression and activity, cell survival, apoptosis and cell cycle. DNA damage was analyzed using the expression of &gamma, H2A.X and phosphorylated ATM. Its tolerance and efficacy were assessed on in vivo xenograft mouse models. We showed that TP5 decreased the activity but not the expression of CDK5 and p35. TP5 alone impaired cell viability and colony formation of glioblastoma cell lines and induced apoptosis. TP5 increased DNA damage by inhibiting the phosphorylation of ATM, leading to G1 arrest. Whereas CDK5 activity is increased by DNA-damaging agents such as temozolomide and irradiation, TP5 was synergistic with either temozolomide or irradiation due to an accumulation of DNA damage. Concomitant use of TP5 and either temozolomide or irradiation reduced the phosphorylation of ATM, increased DNA damage, and inhibited the G2/M arrest induced by temozolomide or irradiation. TP5 alone suppressed the tumor growth of orthotopic glioblastoma mouse model. The treatment was well tolerated. Finally, alone or in association with irradiation or temozolomide, TP5 prolonged mouse survival. TP5 alone or in association with temozolomide and radiotherapy is a promising therapeutic option for glioblastoma.

Lipid nanovesicles (NVs) are the first nanoformulation that entered the clinical use in oncology for the treatment of solid tumors. They are indeed versatile systems which can be loaded with either hydrophobic or hydrophilic molecules, for both imaging and drug delivery, and with high biocompatibility, and limited immunogenicity. In the present work, NVs with a lipid composition resembling that of natural vesicles were prepared using the ultrasonication method. The NVs were successfully loaded with fluorophores molecules (DOP-F-DS and a fluorescent protein), inorganic nanoparticles (quantum dots and magnetic nanoparticles), and anti-cancer drugs (SN-38 and doxorubicin). The encapsulation of such different molecules showed the versatility of the developed systems. The size of the vesicles varied from 100 up to 300 nm depending on the type of loaded species, which were accommodated either into the lipid bilayer or into the aqueous core according to their hydrophobic or hydrophilic nature. Viability assays were performed on cellular models of breast cancer (MCF-7 and MDA-MB-231). Results showed that NVs with encapsulated both drugs simultaneously led to a significant reduction of the cellular activity (up to 22%) compared to the free drugs or to the NVs encapsulated with only one drug. Lipidomic analysis suggested that the mechanism of action of the drugs is the same, whether they are free or encapsulated, but administration of the drugs by means of nanovesicles is more efficient in inducing cellular damage, likely because of a quicker internalization and a sustained release. This study confirms the versatility and the potential of lipid NVs for cancer treatment, as well as the validity of the ultrasound preparation method for their preparation.

A series of biarylaminofluorene-based systems with donor-π-donor (D-π-D) structure have been designed and synthesized in order to study the dependence on the π-conjugated bridge length of the intervalence charge-transfer transitions (IV-CT) and of the electronic coupling between the redox centers. To this purpose cyclic voltammetry, UV/Vis-NIR, fluorescence spectroscopy and computational investigations have been carried out to characterize the electronic structure of the compounds in the neutral as well as in the mono- and dication states. Additionally, a study of related D-π compounds has been performed to elucidate the effect of the interaction between two redox centers. Interestingly it was observed that the mono- and dication species exhibit intense transition bands in the NIR region, in the 10000-15000 cm−1 range, whose intensity depends on the oxidation state and thus it can be reversibly tuned by an applied potential. In a similar way, all compounds show an oxidation state dependent fluorescence which leads to electrofluorochromism. Particularly significant is the mixed valence behavior that provides these systems singular optoelectronic properties, making them excellent active components for electrochromic and electrofluorochromic applications.

Three novel 2D-π-A metal-free organic dyes TK 7 – 9 containing a dibenzofulvene ( DBF ) linked to two thiophene units as the π-bridge, diarylamines with and without alkoxy chains as donor groups and the cyanoacrylic acid moiety as the acceptor and anchoring group were synthesized. The new dyes TK were characterized by optical and electrochemical measurements and density functional theory calculations and were used as sensitizers in liquid dye-sensitized solar cells. The effects of alkoxy-functionalization of donor moiety and of hexyl chain insertion onto one thienyl ring of π-linker on dye properties and performances were investigated. The results discover the dye TK7 , bearing two simple diphenylamine groups without alkoxy chains, exhibits the best behavior in terms of light absorption and cell performance (PCE of 7.9% and photovoltaic parameters of J sc of 17.82 mA cm −2 , V oc of 670 mV and FF of 0.66). Lower power conversion efficiencies of 6.3% and 6.1% were found for TK8 and TK9 , respectively, as a consequence of the presence of the alkoxy chains.

Three fluorenone-derived two-photon fluorescent probes (TK) targeting the lysosomes (TK-Lyso) and mitochondria (TK-Mito1 and TK-Mito2) were synthesized by introducing different diphenylamine moieties into the fluorenone core. The TK dyes showed high biocompatibility and long-term retention, low cytotoxicity, large Stokes shift and good fluorescence quantum yield. The results of the present work disclose a class of organic dyes with potential wide applications as specific and efficient probes for lysosomes and mitochondria in the study of various biological processes.

N-functionalization of 5,6-dihydroxyindole with a hydrophilic triethyleneglycol (TEG) chain provides access to a new class of water-soluble eumelanin-like materials with relatively high dielectric constant and polyelectrolyte behaviour, reflecting enhanced charge transport by in-depth incorporation of hydration networks.

Although it has long been known that the peculiar electronic-ionic conductor behavior of eumelanin is critically dependent on hydration, the detailed mechanisms by which water-polymer interactions control and affect the conduction properties have remained largely obscure. In this paper, we report a remarkable anisotropy and giant polarization effect in a synthetic eumelanin (TEGMe) chemically functionalized with hydrophilic TEG residues. FT-IR analyses of water sorption isotherms and AC measurements were consistent with a microporous structure binding or hosting mainly isolated water molecules. In contrast, similar experiments on a commercial synthetic eumelanin (AMe) used as a reference were suggestive of a bulk macroporous scaffold binding or hosting liquid water. These data disclosed for the first time the differential impact on eumelanin conductivity of vapor, liquid and ice-like forms of water adsorbed onto or embedded into the polymer layer. It is thus demonstrated, for the first time, that hydration controls the conduction properties of eumelanin in a more complex manner than is commonly believed, involving, besides the reported semiquinone comproportionation equilibria, the mode of interaction of water molecules as governed by both the chemical and morphological features of the polymer.

We report on the optical and photo-physical properties of a fluorinated poly(p-phenylenevinylene) derivative, namely poly(2-methoxy-5-[(2-ethylhexyl)oxy]-1,4-phenylenedifluorovinylene) (MEH-PPDFV) and we compare them with those of the well-known non fluorinated reference system, poly(2-methoxy-5-[(2-ethylhexyl)oxy]-1,4-phenylenevinylene) (MEH-PPV) synthesized with the same procedure. Remarkable blue-shifts of absorption and emission spectra of MEH-PPDFV with respect to MEH-PPV are observed, due to the larger distortion from planarity of the fluorinated species. In addition, the blue-shift for optical transitions in absorption spectra is more pronounced than in emission ones, since the molecule conformation in the excited states is more planar than in the ground one. Microsecond photo-induced absorption spectra of MEH-PPDFV reveal three bands possessing spectral properties and/or kinetics different from those observed for MEH-PPV. The assignment of these transitions is provided in terms of free and trapped polarons as well of triplet excitons. Free-polarons have an intrinsic decay constant of 3 μs, while the trapping dynamics has a longer kinetics of 40 μs. The triplet exciton, instead, shows a monoexponetial decay behavior of constant about 10 μs.

A general method to synthesize conjugated molecules with a benzofulvene core is reported. Up to four conjugated substituents have been introduced via a three-step sequence including (1) synthesis of 1,2-bis(arylethynyl)benzenes; (2) exo-dig electrophilic cyclization promoted by iodine; and (3) cross-coupling reaction of the resulting bis-iodobenzofulvenes with organoboron, organotin, or ethynyl derivatives under Pd catalysis. Structural aspects of the new compounds are discussed.

Weak and ultraweak protein-protein association play a role in molecular recognition and can drive spontaneous self-assembly and aggregation. Such interactions are difficult to detect experimentally, and are a challenge to the force field and sampling technique. A method is proposed to identify low-population protein-protein binding modes in aqueous solution. The method is designed to identify preferential first-encounter complexes from which the final complex(es) at equilibrium evolve. A continuum model is used to represent the effects of the solvent, which accounts for short- and long-range effects of water exclusion and for liquid-structure forces at protein/liquid interfaces. These effects control the behavior of proteins in close proximity and are optimized on the basis of binding enthalpy data and simulations. An algorithm is described to construct a biasing function for self-adaptive configurational-bias Monte Carlo of a set of interacting proteins. The function allows mixing large and local changes in the spatial distribution of proteins, thereby enhancing sampling of relevant microstates. The method is applied to three binary systems. Generalization to multiprotein complexes is discussed.

In this review, the main synthetic aspects and properties of fluorinated arylenevinylene compounds, both oligomers and polymers, are summarized and analyzed. Starting from vinyl organotin derivatives and aryl halides, the Stille cross-coupling reaction has been successfully applied as a versatile synthetic protocol to prepare a wide series of π-conjugated compounds, selectively fluorinated on the aromatic and/or vinylene units. The impact of fluoro-functionalization on properties, the solid state organization and intermolecular interactions of the synthesized compounds are discussed, also in comparison with the non-fluorinated counterparts. Luminescent and photovoltaic applications are also discussed, highlighting the role of fluorine on the performance of devices.

Eumelanin-type biopolymers have attracted growing interest in the quest for soft bioinspired functional materials for application in organoelectronics. Recently, a metal-insulator-semiconductor device with a good quality interface was produced by spin coating of a commercial synthetic eumelanin-like material on a dry plasma-modified silicon surface. As a proof-of-concept step toward the design and implementation of next-generation eumelanin-inspired devices, we report herein an expedient chemical strategy to bestow n-type performance to polydopamine, a highly popular eumelanin-related biopolymer with intrinsic semiconductor behaviour, and to tune its electrical properties. The strategy relies on aerial co-oxidation of dopamine with suitable aromatic amines, e.g. 3-aminotyrosine or p- phenylenediamine, leading to good quality black polymeric films. Capacitance-voltage experiments on poly(dopamine/3-aminotyrosine) and poly(dopamine/p-phenylenediamine)-based metal insulator semiconductor devices on p-Si indicated a significant increase in flat band voltage with respect to polydopamine and previous synthetic eumelanin-based diodes. Variations of the flat band voltage under vacuum were observed for each device. These results point to polydopamine as a versatile eumelanin-type water-dependent semiconductor platform amenable to fine tuning of its electronic properties through incorporation of p-conjugating aromatic amines to tailor functionality.

In this article we discuss synthetic routes to organic conjugated oligomers and polymers bearing triple C-C bonds that have been recently developed in our laboratories, based on Pd-catalyzed Csp-Csp 2 coupling reactions. Experimental protocols have been tuned to face synthetic challenges such as the presence in the main conjugated backbone of multifunctional substituents or uncommon conju- gated units. The relevance of the obtained products in terms of properties and applications is also shortly mentioned.

Three new 2D-pi-A dyes (TK4, TK5 and TK6), composed of diarylamine donor groups, a dibenzofulvenethiophene core as the pi-bridge, and a cyanoacrylic acid anchoring group as the acceptor, have been successfully designed, synthesized, and characterized both experimentally and computationally. The performance in DSSC solar cells has been also studied. Octyloxy chains were introduced on the backbone of the dye, in order to increase donor capability, avoid aggregation side effects and increase physical insulation between electrolyte system and the TiO2 layer. The dye containing the octyloxy chains on the donor group and two thiophene ring as an extension of pi-bridge showed the best photovoltaic performance with a maximum of solar energy-to-electricity conversion yield of 7.8% under AM 1.5 irradiation (100 mW/cm(2)). (C) 2016 Elsevier Ltd. All rights reserved.

Three new metal-free organic dyes with the [1]benzothieno[3,2-b]benzothiophene (BTBT) π-bridge, having the structure donor-π-acceptor (D-π-A) and labeled as 19, 20 and 21, have been designed and synthesized for application in dye-sensitized solar cells (DSSC). Once the design of the π-acceptor block was fixed, containing the BTBT as the π-bridge and the cyanoacrylic group as the electron acceptor and anchoring unit, we selected three donor units with different electron-donor capacity, in order to assemble new chromophores with high molar extinction coefficients (ε), whose absorption features well reflect the good performance of the final DSSC devices. Starting with the 19 dye, which shows a molar extinction coefficient ε of over 14,000 M(-1) cm(-1) and takes into account the absorption maximun at the longer wavelength, the substitution of the BFT donor unit with the BFA yields a great enhancement of absorptivity (molar extinction coefficient ε > 42,000 M(-1) cm(-1)), until reaching the higher value (ε > 69,000 M(-1) cm(-1)) with the BFPhz donor unit. The good general photovoltaic performances obtained with the three dyes highlight the suitable properties of electron-transport of the BTBT as the π-bridge in organic chromophore for DSSC, making this very cheap and easy to synthesize molecule particularly attractive for efficient and low-cost photovoltaic devices.

Conjugated polymers with strongly twisted backbones, such as MEHPPV with fluorinated vinylene units (F-MEHPPV), demand a redefinition of the all-important ‘effective conjugation length’ ECL, which we extract here by a facile graphical method. In MEHPPV (being essentially planar), the ECL coincides with the ‘maximum conducive chain length’ MCC and extends over about n ≈ 9 repetition units (RU). In F-MEHPPV, the MCC is similarly long with n ≈ 8, but the ECL localizes on just one RU. The strong twist in F-MEHPPV persists in the excited state, broadening the emission spectrum and quenching the fluorescence with reduced radiative and enhanced non-radiative rates.

A systematic computational investigation on the optical properties of a group of novel benzofulvene derivatives (Martinelli 2014 Org. Lett. 16 3424-7), proposed as possible donor materials in small molecule organic photovoltaic (smOPV) devices, is presented. A benchmark evaluation against experimental results on the accuracy of different exchange and correlation functionals and semi-empirical methods in predicting both reliable ground state equilibrium geometries and electronic absorption spectra is carried out. The benchmark of the geometry optimization level indicated that the best agreement with x-ray data is achieved by using the B3LYP functional. Concerning the optical gap prediction, we found that, among the employed functionals, MPW1K provides the most accurate excitation energies over the entire set of benzofulvenes. Similarly reliable results were also obtained for range-separated hybrid functionals (CAM-B3LYP and wB97XD) and for global hybrid methods incorporating a large amount of non-local exchange (M06-2X and M06-HF). Density functional theory (DFT) hybrids with a moderate (about 20-30%) extent of Hartree-Fock exchange (HFexc) (PBE0, B3LYP and M06) were also found to deliver HOMO-LUMO energy gaps which compare well with the experimental absorption maxima, thus representing a valuable alternative for a prompt and predictive estimation of the optical gap. The possibility of using completely semi-empirical approaches (AM1/ZINDO) is also discussed.

The hyperactivity of the cyclic dependent kinase 5 (CDK5) induced by the activator protein p25 has been linked to a number of pathologies of the brain. The CDK5-p25 complex has thus emerged as a major therapeutic target for Alzheimer's disease (AD) and other neurodegenerative conditions. Experiments have shown that the peptide p5 reduces the CDK5-p25 activity without affecting the endogenous CDK5-p35 activity, whereas the peptide TFP5, obtained from p5, elicits similar inhibition, crosses the blood-brain barrier, and exhibits behavioral rescue of AD mice models with no toxic side effects. The molecular basis of the kinase inhibition is not currently known, and is here investigated by computer simulations. It is shown that p5 binds the kinase at the same CDK5/p25 and CDK5/p35 interfaces, and is thus a non-selective competitor of both activators, in agreement with available experimental data in vitro. Binding of p5 is enthalpically driven with an affinity estimated in the low µM range. A quantitative description of the binding site and pharmacophore is presented, and options are discussed to increase the binding affinity and selectivity in the design of drug-like compounds against AD.

The crystal structure of the cdk5/p25 complex has provided information on possible molecular mechanisms of the ligand binding, specificity, and regulation of the kinase. Comparative molecular dynamics simulations are reported here for physiological conditions. This study provides new insight on the mechanisms that modulate such processes, which may be exploited to control pathological activation by p25. The structural changes observed in the kinase are stabilized by a network of interactions involving highly conserved residues within the cyclin-dependent kinase (cdk) family. Collective motions of the proteins (cdk5, p25, and CIP) and their complexes are identified by principal component analysis, revealing two conformational states of the activation loop upon p25 complexation, which are absent in the uncomplexed kinase and not apparent from the crystal. Simulations of the uncomplexed inhibitor CIP show structural rearrangements and increased flexibility of the interfacial loop containing the critical residue E240, which becomes fully hydrated and available for interactions with one of several positively charged residues in the kinase. These changes provide a rationale for the observed high affinity and enhanced inhibitory action of CIP when compared to either p25 or the physiological activators of cdk5.

This review is an overview of our previous work on the synthesis and properties of poly( p -phenylenevinylene)s (PPVs) selectively fluorinated in different positions of the conjugated backbone. Both the synthetic challenges and the effects of functionalization with fluorine atoms on the optical behavior are discussed, highlighting the peculiarities and the interest of this class of conjugated polymers. A general polymerization protocol for PPVs, that is based on the Pd-catalyzed Stille cross-coupling reaction of bis-stannylated vinylene monomers with aromatic bis-halides, has been successfully extended to the synthesis of selectively fluorinated poly( p -phenylenevinylene)s. The properties of a series of these PPVs differing in the number and positions of the fluorine atoms on the conjugated backbone have been studied, even in comparison with the non-fluorinated counterparts. The intriguing optical features of the resulting materials are discussed considering not only the role of the electronic and steric effects induced by the fluorine substituents, but also the impact of the fluorination on the solid state organization and intermolecular interactions.

Fully fluorinated arylenevinylene polymers have been synthesized via a methodology based on the Stille cross-coupling reaction and characterized by FTIR spectroscopy and MALDI-TOF mass spectrometry. Investigation of thin film properties by cyclic voltammetry and ellipsometry shows that complete substitution of hydrogen atoms with fluorine atoms on the conjugated backbone of the poly(arylenevinylene)s results in a strong increase of the band gap.

Poly(2′,5′-dioctyloxy-4,4′,4″-terphenylenevinylene) with ( E ) configuration of the vinylene double bonds was prepared by Suzuki–Miyaura polymerization of ( E )-4,4′-dibromostilbene and 2,5-dioctyloxy-1,4-benzenediboronic acid. Attempts to extend this simple procedure to the synthesis of the polymer with ( Z ) configuration, starting from ( Z )-4,4′-dibromostilbene, were unsuccessful. However, the use of ( Z )-4,4′-diiodostilbene and a careful choice of Pd catalyst and experimental conditions, lead to a material with a >95/ Z )/( E ) ratio of vinylene units. The investigation of optical properties of both the ( E ) and ( Z ) polymers evidenced that ( Z ) linkages act as defects which reduce the effective conjugation length in the polymer backbone.

Poly(arylenevinylene) polymers bearing fluorine atoms in the vinylene units were obtained by a Stille cross-coupling reaction of (E)-(1,2-difluoro-1,2-ethenediyl)bis(tributylstannane) with diiodoaryl derivatives. The introduction of fluorine atoms on the double bond of the stannane leads to polymers with relatively high molecular weights. Furthermore, the presence of fluorinated vinylene units changes the optical properties of the polymers and shifts the emission towards the blue region of the visible spectrum. A fluorinated analogue of MEH-PPV was obtained, and it shows photoluminescence that is considerably blueshifted, also in the solid state, relative to that found for nonfluorinated MEH-PPV and to other PPVs with fluorinated double bonds.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

The review addresses features of special interest concerning two classes of functionalized semiconducting polymers: poly(aryleneethynylene)s (PAEs) bearing biomolecules as chiral nonracemic pendant groups and poly(phenylenevinylene)s (PPVs), which are fluorinated in various positions of the repeating units. Molecular design and choice of specific substituents, synthetic protocols, and the effect of functionalization on properties of the polymers both in solution and in the solid state are discussed.

A conjugated alternating copolymer containing norbornadiene and bis(ethynylene)phenylene units was prepared by the Cassar-Heck-Sonogashira cross-coupling reaction. Its electroluminescence was tested in a device, and its fluorescence colour could be tuned by light-induced norbornadiene-quadricyclane isomerization.

Over the past decade synthetic melanins, melanin-like polymers and melanin-based copolymers have been the focus of growing attention as soft biocompatible functional materials for engineering high performance, low cost optoelectronic devices, such as memory devices, light emitting diodes and field effect transistors. The unique combination of physicochemical properties of melanins, such as broad band absorption in the UV-visible range, intrinsic free radical character, water-dependent hybrid ionic-electronic conductor behaviour and excellent biocompatibility, have inspired use of melanic polymers as valuable functional materials for organic bioelectronics. However, several gaps and issues still hinder rapid progress of melanin-based organic electronics and bioelectronics, including in particular the limited contribution of electronic conductivity and current decay with time under biasing. The aim of this paper is to provide an overview of the structural and optoelectronic properties of melanins and to bring to focus current gaps and challenges in the development of melanin-based materials for bioelectronics. Starting from commercial samples, the paper surveys different melanin-type materials with special emphasis on the potential of polydopamine (pDA), a highly adhesive mussel-inspired melanin-type platform, for incorporation in optoelectronic devices. Simple chemical tailoring procedures for engineering pDA-based n-type polymers and photoresponsive materials for photocapacitive sensors are eventually illustrated.

A method is proposed to study protein-ligand binding in a system governed by specific and non-specific interactions. Strong associations lead to narrow distributions in the proteins configuration space; weak and ultra-weak associations lead instead to broader distributions, a manifestation of non-specific, sparsely-populated binding modes with multiple interfaces. The method is based on the notion that a discrete set of preferential first-encounter modes are metastable states from which stable (pre-relaxation) complexes at equilibrium evolve. The method can be used to explore alternative pathways of complexation with statistical significance and can be integrated into a general algorithm to study protein interaction networks. The method is applied to a peptide-protein complex. The peptide adopts several low-population conformers and binds in a variety of modes with a broad range of affinities. The system is thus well suited to analyze general features of binding, including conformational selection, multiplicity of binding modes, and nonspecific interactions, and to illustrate how the method can be applied to study these problems systematically. The equilibrium distributions can be used to generate biasing functions for simulations of multiprotein systems from which bulk thermodynamic quantities can be calculated.

Ring the changes: Experimental Raman spectra of fluorinated and non-fluorinated polyphenylenevinylenes are assigned according to quantum chemical calculations for oligomer model systems [picture: see text]. Characteristic differences in the spectra can be traced back to strong inter-ring distortion of the fluorinated compounds.The Raman spectrum of poly{2-methoxy-5-[(2-ethylhexyl)oxy]-1,4-phenylenedifluorovinylene} (MEH-PPDFV) is reported and compared with that of a well-known non-fluorinated reference polymer, namely poly{2-methoxy-5-[(2-ethylhexyl)oxy]-1,4-phenylenevinylene} (MEH-PPV). The Raman spectra of both polymers are assigned on the basis of density functional theory calculations of the corresponding oligomers. The main differences between vinylene fluorinated and non-fluorinated structures deal with the intensity, frequency shift and broadening of C--C vinylene stretching. Additional differences concern the relative intensities of C-C phenylene and vinylene stretching as well as the deformation modes in the range 1250-1350 cm(-1). It is shown that these effects are due to the larger distortion from planarity of the fluorinated polymer, compared with the non-fluorinated counterpart, induced by repulsive interactions between the fluorine atoms on the vinylene units and the oxygen atoms of the alkoxy groups on the aromatic rings.

Background Selective imaging of lysosomes by fluorescence microscopy using specific fluorescent probes allows the study of biological processes and it is potentially useful also for diagnosis. Lysosomes are involved in numerous physiological processes, such as bone and tissue remodeling, plasma membrane repair, and cholesterol homeostasis, along with cell death and cell signaling. Despite the great number of dyes available today on the market, the search for new fluorescent dyes easily up-taken by cells, biocompatible and bearing bright and long-lasting fluorescence is still a priority. Methods Two thiophene-based fluorescent dyes, TC1 and TC2, were synthetized as lysosome-specific probes. Results The new dyes showed high selectivity for fluorescent staining and imaging of lysosomes and disclosed high photostability, low toxicity and pH insensitivity in the range 2–10. Conclusions The TC dyes exhibited high co-localization coefficients (> 95%) and moderate quantum yields. They showed high biocompatibility and long-term retention, important features for biological applications. General significance The results of the present work disclose a new class of organic dyes with potential wide applications as specific and efficient lysosome probes in the study of various biological processes.

Benzofulvenes-based monomers have been synthesized for the first time and have been polymerized by means of electrochemical methods onto different electrodic materials. Morphological investigation has been performed by using SEM; electrical and optical properties have been studied by means of both cyclic voltammetry, optical absorption and spectroelectrochemical techniques. Finally, solid state electrochromic devices have been fabricated. They have displayed high optical contrast.

Colloidal white emitting nanostructures were successfully fabricated by covalently binding a blue emitting oligofluorene at the surface of silica beads, that incorporate orange luminescent colloidal CdSe@ZnS quantum dots (QDs). White light was achieved by carefully tuning the size of the QDs to complementarily match the emission color of the blue fluorophore and taking into account the delicate balance between the emission of the QDs in the core of the silica beads and the amount of the organic dye bound to the silica surface. The proposed approach is highly versatile as it can be extended to the fabrication of a variety of luminescent hybrid nano-objects, playing with the complementarity of the emission color of the inorganic and organic fluorophores at the nanoscale. This journal is © the Partner Organisations 2014.

A white emitting copolymer with the polyphenylenevinylene (PPV) structure is obtained via the Stille cross-coupling reaction. Substitution of hydrogen atoms with fluorine atoms on the vinylene units of poly(1,4-dialkoxyphenylenevinylene) shifts the emission from orange-red to blue. White emission is obtained by combining dialkoxyphenylenedifluorovinylene and dialkoxyphenylenevinylene units in proper ratio. The two complementary emitters are obtained separately by Stille polymerization reaction. Then, the two reaction mixtures are combined without purification in different ratios and further reacted in similar experimental conditions. A white luminescent material is obtained using 99/1 mixing ratio. OLED devices fabricated with this copolymer shows near-white emission with CIE (0.30, 0.40) and excellent stability in the range 10–200 cd/m 2 .

The electrical transport across a biomimetic interface made up of spin coated melanin layers on nanotextured silicon surfaces with different texturing features and wetting properties is discussed. Nanotexturing allows, under certain conditions, the melanin to anchor better on a hydrophobic silicon surface, overcoming the hydrophilic melanin–hydrophobic silicon interface issue. The feature of the electrical signal transduction across such a structure was studied by impedance spectroscopy and found to be influenced by the nano-texturing chemistry and surface morphology. The effects of a voltage pulse, as external stimulus modifying the electrical transport mechanisms, and retention of the subsequently achieved carrier transport conditions have been elucidated. The results suggest a possible exploiting of this circuit element for bio and environmental molecules’ sensing.

Inspired by the powerful photosensitizing properties of the red hair pigments pheomelanins, a photoresponsive cysteine-containing variant of the adhesive biopolymer polydopamine (pDA) is developed via oxidative copolymerization of dopamine (DA) and 5-S-cysteinyldopamine (CDA) in variable ratios. Chemical and spectral analysis indicate the presence of benzothiazole/benzothiazine units akin to those of pheomelanins. p(DA/CDA) copolymers display impedance properties similar to those of biological materials and a marked photoimpedance response to light stimuli. The use of the p(DA/CDA) copolymer to implement a solution-processed hybrid photocapacitive/resistive metalinsulator- semiconductor (MIS) device disclosed herein is the fi rst example of technological exploitation of photoactive, red-hair-inspired biomaterials as soft enhancement layer for silicon in an optoelectronic device. The bio-inspired materials described herein may provide the active component of new hybrid photocapacitive sensors with a chemically tunable response to visible light.

Ullmann-like reductive coupling of 1,4-diiodo-2,3,5,6-tetrafluorobenzene, promoted by copper(I) thiophene-2-carboxylate in N -methylpyrrolidinone at room temperature, followed by treatment with lithium aluminum hydride in THF, allowed us to obtain fluorinated poly( para -phenylene) oligomers containing up to five aromatic rings with hydrogen atoms as terminal groups.

Anthocyanins, extracted from grape skin ( Vitis vinifera ), were dissolved in ultrapure aqueous subphase and an oligophenylenevinylene derivative was spread on the subphase surface. Such oligomer was chosen as anionic counterpart of hydrosoluble anthocyanins in order to perform a Langmuir–Schafer film of the dyad. Interface interactions between oligophenylenevinylene derivative and anthocyanins were studied by Brewster angle microscopy and reflection spectroscopy. Additionally, the oligomer exhibits a chemical structure able to ensure an enhancement of the stability under UV–visible irradiations of the film of the dyad without any variation of the natural pigment absorption in the visible range. The visible spectra of cast anthocyanins film and Langmuir–Schafer oligomer/anthocyanins film after exposure to 254 nm irradiation showed a remarkable increase of the film stability, probably due to the screening effect of the oligomer. Preliminary test of a Langmuir–Schafer film of oligophenylenevinylene derivative/anthocyanins as a herbicide sensor showed that sensing is completely reversible, stable and repeatable.

This review reports a survey of our recent results on the synthesis of arylenevinylene polymers and oligomers selectively functionalized with fluorine atoms on aromatic and/or vinylene units. The synthetic methods developed are based on Pd-catalyzed organometallic cross-coupling reactions and in particular on the Stille coupling between vinyl organotin derivatives and aromatic halides. Several compounds have been synthesized, which differ for the number and position of the fluorine atoms on the conjugated backbone, even combined with other functional groups. The effects of fluorination on optical properties both in solution and solid state are discussed.

Nowadays considerable efforts are devoted to the synthesis of low bandgap conjugated polymers for application in organic polymer solar cells. A large variety of low bandgap polymers are prepared by alternating copolymerization of electron-donating donor and electron-withdrawing acceptor units. The interaction between these two units can reduce the polymer bandgap, increasing the sunlight absorption. Benzothiadiazole is commonly used as acceptor block unit in low bandgap polymers. In this contribution we investigate the supramolecular organization and optical properties of thin films of conjugated polymers consisting of benzothiadiazole and thiophene with electron-withdrawing difluorovinylene, and electron-donating vinylene substituents. Atomic force microscopy and spectroscopic ellipsometry are exploited for the analysis of the morphology and optical transitions, respectively. It is found that F-atoms in the vinylene unit yield a blue-shift of the absorption peaks of 0.2 eV respect to the hydrogenated polymer and an increase in the absorption coefficient of fluorinated polymers, which indicates their potential application as photovoltaic material. The morphology evolution of the conjugated polymers blended with a fullerene derivate ([6,6]-phenyl C61-butyric acid methyl ester, PCBM) is also investigated by atomic force microscopy.

The use of an amphiphilic aryleneethynylene fluorophore as a plasma membrane marker in fixed and living mammalian cells and liposome model systems is demonstrated. We show here that the optical properties of the novel dye are almost independent on pH, in the range 5.0–8.0. Spectroscopic characterization performed on unilamellar liposomes ascertained that the fluorescence intensity of the aryleneethynylene fluorophore greatly increases after incorporation in lipidic membranes. Experiments performed on different mammalian cells demonstrated that the novel membrane marker exhibits fast staining and a good photostability that make it a suitable tool for live cell imaging. Importantly, the aryleneethynylene fluorophore was also shown to be a fast and reliable blue membrane marker in classical multicolor immunofluorescence experiments. This study adds new important findings to the recent exploitation of the wide class of aryleneethynylene molecules as luminescent markers for biological investigations.

Dr. M. Ambrico , Dr. P. F. Ambrico CNR-Istituto di Metodologie Inorganiche e dei Plasmi-UOS di Bari70125 Bari, Italy E-mail: marianna.ambrico@ba.imip.cnr.it Dr. A. Cardone , Dr. S. R. Cicco CNR-Istituto di Chimica dei Composti OrganoMetallici-UOS di Bari70125 Bari, Italy Ligonzo , Dr. . T Prof. Augelli . V Dipartimento Interateneo di FisicaUniversita degli Studi di Bari “Aldo Moro”70125 Bari, Italy Dr. R. Di Mundo , Prof. G. M. arinola F Dipartimento di ChimicaUniversita degli Studi di Bari “Aldo Moro”70125 Bari, Italy

Functionalization with fluorine atoms represents a versatile structural modification to finely tune both the emission colour and the electronic properties of organic and organometallic electroluminescent compounds. This paper reports an overview of our systematic investigation on the design and synthesis of the fluorinated version of two important classes of materials for organic light emitting diodes (OLEDs), namely poly(arylenevinylene)s and phosphorescent phenylpyridine Iridium complexes. Synthetic pathways based on organometallic methodologies affording selectively fluorinated molecular structures will be discussed together with a summary of the effect of fluorination on the optical properties of the resulting materials. In particular we will highlight the possibilities offered by the organometallic methodologies as straightforward and resourceful tools to provide a wide series of fluorinated molecular architectures with high regio- and stereoselectivity, mild experimental conditions and good yields.

Ullmann-like reductive coupling of 1,4-diiodo-2,3,5,6-tetrafluorobenzene, promoted by copper(I) thiophene-2-carboxylate in N -methylpyrrolidinone at room temperature, followed by treatment with lithium aluminum hydride in THF, allowed us to obtain fluorinated poly( para -phenylene) oligomers containing up to five aromatic rings with hydrogen atoms as terminal groups.

There has been growing interest in developing new semiconducting polymers for applications in optoelectronics (OLEDs) due to their exceptional processability and appealing characteristic of manipulating electronic and optical properties by tuning of molecular structure and self-assembling. This study is an investigation on the interplay among supermolecular organization and optical properties of thin films of the poly[2-(2-ethylhexyloxy)-5-methoxy]-1, 4-phenylenedifluorovinylene (MEH-PPDFV) conjugated polymer, which has fluorinated vinylene units. This interplay is elucidated exploiting atomic force microscopy, spectroscopy ellipsometry, photoluminescence and electroluminescence. Thin films of MEH-PPDFV have been deposited by drop casting on indium-tin-oxide (ITO), quartz and glass substrates. The dependence of polymer chains self-organization and morphology on substrate surface is presented. Furthermore, it is demonstrated that the presence of F-atoms in the vinylene units of the MEH-PPDFV yields a blue optical band gap with the maximum of the fundamental HOMO-LUMO transition at 331 nm and photoluminescence at 458 nm. The OLED built with the above polymer shows a very stable blue-greenish electroluminescence that is also achieved at 504 nm.

Hysteresis behaviour of the current–voltage characteristics collected on spin coated synthetic eumelanin layer embedded in the Au/eumelanin/ITO/glass structure is shown. The effect has been observed under dark both in air and vacuum environment and its magnitude has been found related to the eumelanin hydration state. Moreover, in vacuum and under white light illumination, enhancement of the hysteresis loop area respect to those collected under dark has been observed. Space charge storage and charge trapping/detrapping as possible mechanisms responsible of the observed current–voltage behaviour are discussed. Preliminary experimental results have evidenced the possible integration of eumelanin layers in electro-optical charge storage based memory devices.

Blue-light-emitting poly(p-phenylene vinylene)s with fluorinated vinylene units are presented. It is demonstrated that self-aggregation governs the strength and polarization of the absorption spectra of thin films of these polymers. This indicates that self-assembly of the polymer chains in the films provides a means of tuning the electronic and optical properties of the pi-conjugated systems.

Tetracyanoquinodimethane (TCNQ) and anthraquinone derivatives were synthesized to coordinate the surface of CdSe quantum dots (QDs). These electroactive surfactants are specifically designed to promote the interactions of organic semiconductor quantum dots with a polymer matrix. Starting from colloidal CdSe nanocrystals covered with a layer of TOPO, a process of ligand exchange is worked out in order to obtain new nanocrystal-surfactant heterostructures. We demonstrate that the fluorescence of the nanocrystals is completely quenched upon the formation of the heterostructure CdSe/surfactant indicating an efficient carrier transfer from the QDs to the surfactant.

Oligoarylenevinylenes with fluorine atoms in the vinylene units and side-chains with a range of polarities bonded to the aryl rings, have been synthesized via a methodology based on the Stille cross-coupling reaction. All compounds were stereoselectively synthesized with trans double bonds.

A straightforward and general procedure for the introduction of aryl and vinyl substituents in the 5 or 7 position of 8-hydroxyquinoline has been developed. The methodology presented is based upon the Suzuki cross-coupling reaction of aryl or vinyl halides with 5-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)quinolin- 8-ol or 7-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)quinolin-8- ol, respectively, that have been obtained regioselectively starting from 8-hydroxyquinoline