Tuning the Electronic Properties of Bridged Dithienyl-, Difuryl-, Dipyrrolyl-Vinylene as Precursors of Small-Bandgap Conjugated Polymer.

Optoelectronic properties of linear π-conjugated polymers/oligomers are of great importance for the fabrication of organic photonic and electronic devices. To this end, the π-conjugated polymers/oligomers need to meet both optoelectronic and key structural properties in order to fulfill their implementation as active components. In particular, they need to possess low bandgap and high thermal, conformational, and photochemical stabilities. So far, several strategies have been developed to attain such requirements including the covalent and non-covalent rigidification concepts of the π-conjugated systems. On the basis of these findings, we describe herein the theoretical studies of novel series of covalently bridged derivatives demonstrating the benefits of the strategy. Comparison of these derivatives with compounds previously described in the literature highlights enhanced optoelectronic properties and behaviors that would be beneficial for the construction and development of new linear π-conjugated polymers.

Self-Assembled Monolayers of Push-Pull Chromophores as Active Layers and Their Applications.

In recent decades, considerable attention has been focused on the design and development of surfaces with defined or tunable properties for a wide range of applications and fields. To this end, self-assembled monolayers (SAMs) of organic compounds offer a unique and straightforward route of modifying and engineering the surface properties of any substrate. Thus, alkane-based self-assembled monolayers constitute one of the most extensively studied organic thin-film nanomaterials, which have found wide applications in antifouling surfaces, the control of wettability or cell adhesion, sensors, optical devices, corrosion protection, and organic electronics, among many other applications, some of which have led to their technological transfer to industry. Nevertheless, recently, aromatic-based SAMs have gained importance as functional components, particularly in molecular electronics, bioelectronics, sensors, etc., due to their intrinsic electrical conductivity and optical properties, opening up new perspectives in these fields. However, some key issues affecting device performance still need to be resolved to ensure their full use and access to novel functionalities such as memory, sensors, or active layers in optoelectronic devices. In this context, we will present herein recent advances in π-conjugated systems-based self-assembled monolayers (e.g., push-pull chromophores) as active layers and their applications.

Synthesis and antimicrobial testing of 5-fluorouracil derivatives.

Antibiotic resistance has increased the demand for novel treatments against multidrug-resistant microorganisms. In the research literature, 5-fluorouracil (5-FU) was proposed as an alternative due to its intrinsic antibacterial property. However, given its toxicity profile at high doses, its use in antibacterial therapy is dubious. In the quest for improving the efficacy of 5-FU, the present study intends to synthesise 5-FU derivatives and assess their susceptibility and mechanism against pathogenic bacteria. It was found that the compounds having tri-hexylphosphonium substitution on both nitrogen groups of 5-FU (6a, 6b and 6c) had considerable activity against both Gram-positive and Gram-negative bacteria. Among the active compounds, those with an asymmetric linker group 6c were found to have higher antibacterial efficacy. However, no conclusive efflux inhibition activity was found. As elucidated by electron microscopy studies, these self-assembling active phosphonium-based 5-FU derivatives caused considerable septal damage and cytosolic alterations in Staphylococcus aureus cells. In Escherichia coli, these compounds triggered plasmolysis. Interestingly, the minimal inhibitory concentration (MIC) of the most potent 5-FU derivative 6c remained constant, regardless of the bacteria's resistance profile. Further analysis revealed that compound 6c generated significant alterations in membrane permeabilization and depolarization in S. aureus and E. coli cells at the MIC. Compound 6c was found to substantially impede bacterial motility, suggesting its importance in regulating bacterial pathogenicity. Additionally, the nonhaemolytic activity of 6c suggested that it could be a potential therapeutic option for treating multidrug-resistant bacterial infections.

Quinones as an Efficient Molecular Scaffold in the Antibacterial/Antifungal or Antitumoral Arsenal.

Quinone-based compounds constitute several general classes of antibiotics that have long shown unwavering efficiency against both Gram-positive and Gram-negative microbial infections. These quinone-based antibiotics are increasingly popular due to their natural origins and are used in natural beverages from herbs or plants in African, Chinese and Indian traditional medicines to treat and prevent various diseases. Quinone-based antibiotics display different bioactive profiles depending on their structures and exert specific biocidal and anti-biofilm properties, and based on recent literature, will be discussed herein.

Nanoarchitectonics of Electrically Activable Phosphonium Self-Assembled Monolayers to Efficiently Kill and Tackle Bacterial Infections on Demand.

Prosthetic implants are widely used in dentistry and orthopedics and, as a result, infections can occur which cause their removal. Therefore, it is essential to propose methods of eradicating the bacteria that remain on the prosthesis during treatment. For this purpose, it is necessary to develop surfaces whose antibacterial activity can be controlled. Herein, we designed innovative and smart phosphonium self-assembled monolayer (SAM) interfaces that can be electrically activated on demand for controlling bacterial contaminations on solid surfaces. Upon electroactivation with a low potential (0.2 V for 60 min., conditions determined through a DOE), a successful stamping out of Gram-positive and Gram-negative bacterial strains was obtained with SAM-modified titanium surfaces, effectively killing 95% of Staphylococcus aureus and 90% Klebsiellapneumoniae. More importantly, no toxicity towards eukaryotic cells was observed which further enhances the biocompatible character of these novel surfaces for further implementation.

Phosphonium-ammonium-based di-cationic ionic liquids as antibacterial over the ESKAPE group.

Emergence of antibioresistance is currently a major threat of public health worldwide. Hence there is an urge need of finding new antibacterial material. Herein, we report a simple and eco-friendly method to synthesize homo and heterodicationic ionic liquids based on quaternary phosphonium and ammonium salt. In order to investigate the structure activity relationship (SAR) we measured the MICs of a series of 16 derivatives with structural variations (nature of cations and counter-ions, size of linker and alkyl side chains as well as structural symmetry) over a range of Gram-positive and Gram-negative bacterial strains from the ESKAPE group. Some of the tested structures exhibit high antimicrobial activities (MIC = 0.5 mg/L) and are active over a wide range of bacteria from Gram-positive to Gram-negative. Overall, these results reveal the strong potential of di-cationic derivatives as antibacterial agents and the determination of activities from structural features gives decisive information for future synthesis of such di-cationic structures for biocidal purpose.

Antibacterial activities of mono-, di- and tri-substituted triphenylamine-based phosphonium ionic liquids.

We report the synthesis of new mono, di and tri phosphonium ionic liquids and the evaluation of their antibacterial activities on both Gram-positive and Gram-negative bacteria from the ESKAPE-group. Among the molecules synthesized some of them reveal a strong bactericidal activity (MIC = 0.5 mg/L) for Gram-positive bacteria (including resistant strains) comparable to that of standard antibiotics. A comparative Gram positive and Gram negative antibacterial activities shows that the nature of counter-ion has no significant effects. Interestingly, the increase of phosphonium lateral chains (from 4 to 8 carbons) results in a decrease of antibacterial activities. However, the increase of the spacer length has a positive influence on the activity on both Gram-positive and Gram-negative bacteria except for E. aerogenes. Finally, the increased charge density has no effect on the Gram-positive antibacterial activities (MIC between 2 and 4 mg/L) but seems to attenuate (except for P. aeruginosa) the discrimination between Gram-positive and Gram-negative. Overall these results suggest a unique mechanism of action of these triphenylamine-phosphonium ionic liquid derivatives.

Bacterial anti-adhesion activity based on the electrochemical properties of polymethacrylates bearing ferrocenyl pendant groups.

Much current research is focused on preventing and controlling the natural process of colonization by marine organisms of surfaces submerged in seawater. Previously, the authors' laboratory has reported the synthesis and the full physico-chemical characterization of homopolymers obtained from 1-ferrocenylmethyl methacrylate (FMMA), 2-(ferrocenylmethoxy)ethyl methacrylate (FMOEMA), and 3-(ferrocenylmethoxy)propyl methacrylate (FMOPMA). Here, the bacterial anti-adhesion activity of these homopolymers (pFMMA, pFMOEMA and pFMOPMA) is reported when stimulated in 96-well microplates containing a printed electrochemical cell in each well. Polymers were deposited on the printed carbon working electrode of each well in two columns each comprising eight wells. Their electrochemical anti-adhesion properties were evaluated by inoculating a marine biofilm forming bacterial strain, Pseudoalteramonas lipolytica, in each well and then applying recurrent scans for 15 h. The results revealed an intrinsic anti-adhesion activity of all the polymers. This activity was amplified by a factor of 10 when potential recurrent scans were applied.

Subpicomolar Iron Sensing Platform Based on Functional Lipid Monolayer Microarrays.

We report herein the fabrication of novel microarrays based on air-stable functional lipid monolayers over silicon using a combination of e-beam lithography and lift-off. We demonstrate these microarrays can be use as ultrasensitive platform for Kelvin probe force microscopy in sensing experiments. Specificity of the detection is given by the functional group grafted at the lipid headgroup. The arrays developed for the detection of ferric ions, Fe(3+), using a γ-pyrone derivative chelator, demonstrate subpicomolar limit of detection with high specificity. In addition, the technique takes advantage of the structure of the array with the silicon areas playing the role of reference for the measurement, and we determine critical pattern dimensions below which the probe size/shape impacts the measured results.

Highly specific and reversible fluoride sensor based on an organic semiconductor.

A novel sulfonamide-conjugated benzo-[2,1-b:3,4-b']bithiophene semiconductor has been designed and synthetized in order to develop a probe for specific detection of anions both in the homogeneous (solution) and heterogeneous phase. Its photophysical and electrochemical data were reported in this study. On the basis of the optical and NMR titrations analysis, the chelator was found to be highly selective for fluoride compared to others anions (Ka = 1.6 × 10(4) M(-1) in dimethyl sulfoxide (DMSO)). In addition, from an intricate sample, the novel chelator shows exceptional specificity toward fluoride and reveals a complete reversibility after addition of trifluoroacetic acid (TFA). Sensing films were obtained by electrochemical polymerization of the probe on an electrode surface, which clearly show effective detection of fluoride.

Arylthio-substituted coronenes as tailored building blocks for molecular electronics.

The electron transport through molecules in molecular devices is typically influenced by the nature of the interfaces with the contacting electrodes and by the interactions between neighbouring molecules. It is a major goal of molecular electronics to adjust the electronic function of a molecular device by tailoring the intrinsic molecular properties and the interfacial and intermolecular interactions. Here, we report on the tunability of the electronic properties of coronene derivatives, namely dodecakis(arylthio)coronenes (DATCs), which are found to exhibit a three-dimensional aromatic system. Scanning tunnelling microscopy (STM), spectroscopy (STS) and simulations based on the density functional theory (DFT) are employed to characterize the structural and electronic properties of these molecules deposited on Au(111) surfaces. It is shown that modifications of the peripheral aryl-groups allow us to specifically affect the self-assembly and the charge transport characteristics of the molecules. Molecular assemblies like supramolecular wires with highly delocalized orbitals and single molecules with molecular "quantum dot" characteristics are obtained in this way.

Naked-Eye Chromogenic Test Strip for Cyanide Sensing Based on Novel Phenothiazine Push-Pull Derivatives.

Monitoring and detection of cyanide are of crucial interest as the latter plays versatile roles in many biological events, is ubiquitous in environment, and responsible for several acute poisoning and adverse health effects if ingested. We describe herein the synthesis and characterization of novel phenothiazine-based push-pull chromogenic chemosensors suitable for naked eye cyanide sensing. Indeed, specific detections were achieved for cyanide with a LOD of ca 9.12 to 4.59 µM and, interestingly, one of the new chemosensors has also revealed an unprecedented affinity for acetate with a LOD of ca 2.68 µM. Moreover, as proof of concept for practical applications, a paper test strip was prepared allowing its use for efficient qualitative naked eye cyanide sensing.

Recent Electrochemical/Electrical Microfabricated Sensor Devices for Ionic and Polyionic Analytes.

The recent technological advances combined with the development of new concepts and strategies have revolutionized the field of sensor devices, allowing access to increasingly sophisticated device structures associated with high sensitivities and selectivities. Among them, electrochemical and electrical sensors have gained the most interest because they offer unique intrinsic characteristics and meet the requirements to be integrated in more sophisticated devices including microfluidics or lab-on-chips, opening access to multiplex and all-in-one detection devices. In the present article, we outline and provide a short and concise overview on the most recent achievements in the field of electrical detection of ionic species as they display versatile roles in many important biological events and are ubiquitous in environment.

Novel and Innovative Interface as Potential Active Layer in Chem-FET Sensor Devices for the Specific Sensing of Cs.

An innovative novel interface has been designed and developed to be used as a potential active layer in chemically sensitive field-effect transistor (Chem-FET) sensor devices for the specific sensing of Cs+. In this study, the synthesis of a specific Cs+ probe based on calix[4]arene benzocrown ether, its photophysical properties, and its grafting onto a single lipid monolayer (SLM) recently used as an efficient ultrathin organic dielectric in Chem-FETs are reported simultaneously. On the basis of both optical and NMR titration experiments, the probe has shown high selectivity and specificity for Cs+ compared to interfering cations, even if an admixture is used. Additionally, Attenuated Total Reflectance Fourier Transform Infra Red (ATR-FTIR) spectroscopy was successfully used to characterize and prove the efficient grafting of the probe onto a SLM and the formation of the innovative novel sensing layer.

Polysulfurated pyrene-cored dendrimers: luminescent and electrochromic properties.

We have synthesized a novel class of dendrimers, consisting of a polysulfurated pyrene core with appended poly(thiophenylene) dendrons (PyG0, PyG1, and PyG2, see Scheme 1), which exhibit remarkable photophysical and redox properties. In dichloromethane or cyclohexane solution they show a strong, dendron-localized absorption band with a maximum at around 260 nm and a band in the visible region with a maximum at 435 nm, which can be assigned to the pyrene core strongly perturbed by the four sulfur substituents. The dendrimers exhibit a strong (Phi=0.6), short-lived (tau=2.5 ns) core-localized fluorescence band with maximum at approximately 460 nm in cyclohexane solution at 293 K. A strong fluorescence is also observed in dichloromethane solution at 293 K, in dichloromethane/chloroform rigid matrix at 77 K, and in the solid state (powder) at room temperature. The dendrimers undergo reversible chemical and electrochemical one-electron oxidation with formation of a strongly colored deep blue radical cation. A second, reversible one-electron oxidation is observed at more positive potential values. The photophysical and redox properties of the three dendrimers are finely tuned by the length of their branches. The strong blue fluorescence and the yellow to deep blue color change upon reversible one-electron oxidation can be exploited for optoelectronic devices.

Glycosylated asterisks are among the most potent low valency inducers of Concanavalin A aggregation.

A new class of sulfurated, semi-rigid, radial and low-valent glycosylated asterisk ligands with potential dual function as ligand and probe has some of the highest inhibition potencies of Con A-induced hemagglutination, by using a cross-linking mechanism of Con A which amplifies the enhancement to near nanomolar concentrations with the alpha-d-mannose asterisk.

Synthesis of small gold nanoparticles: Au(I) disproportionation catalyzed by a persulfurated coronene dendrimer.

Gold nanoparticles with average diameter of 1.0 nm and narrow size distribution can be easily obtained by disproportionation of Au(+) ions, in the presence of a persulfurated coronene dendrimer that favors encounters between Au(+) ions and protects the resulting small nanoparticles from further aggregation.

Persulfurated aromatic compounds.

Persulfurated arenes have been known for about 50 years but they were underexploited in chemistry in spite of facile, mild, and high-yielding syntheses. Their properties (redox potentials, UV/Vis absorption, conductivity, nonlinear optical properties, etc.) are mainly due to the aromaticity of the ring with sp2-hybridized carbon atoms and to the electronic contribution from numerous divalent sulfur ligands, which also stabilize negative or positive charges. The characteristic conformational patterns of the sulfur ligands often facilitate preorganization in supramolecular assemblies, with or without thiophilic metal cations, for designing redox sensors, ion-selective membranes, clathrates, organic conductors, nonlinear optical materials, liquid crystals, coordination polymers, and bioinorganic systems. A new class of supramolecules with various molecular shapes such as asterisks, chains, wheels, and windmills were reported.

Alternated quinoid/aromatic units in terthiophenes building blocks for electroactive narrow band gap polymers. Extended spectroscopic, solid state, electrochemical, and theoretical study.

We report here the synthesis of three novel pi-conjugated heterocyclic mixed trimers that contain two electron-donating 3,4-ethylenedioxy-2-thienyl (EDOT) units covalently attached to a central proquinoid electron-accepting thienopyrazine moiety (two of these narrow-HOMO-LUMO gap D-A-D compounds also bear hexyl side chains attached either to the outermost alpha positions of the EDOT end rings or to the beta positions of the pyrazine fused ring). The modification of the terthiophene structure upon EDO, pyrazine, and hexyl substitutions has been treated in detail with spectroscopic and theoretical arguments. Solid-state properties reveal the occurrence of short intramolecular contacts between heteroatoms of adjacent rings. The analysis of the structure of the pi-conjugated backbone of each molecule is consistent with a partial quinoid-like pattern which partially reverts to be subtly more aromatic depending on the topology of the positive inductive effect of the hexyl chains. This quinoidization is a consequence of the appearance of a D(EDOT)-->A(PyT)<--D(EDOT) intramolecular charge transfer which further polarizes the structure. The same chemical concepts have been applied to address their electrochemical behavior. The three mixed trimers exhibit amphoteric properties due to the combination of electron acceptor and donor groups. Given their relative low HOMO-LUMO energy gap, these trimers promise to be good candidates for obtaining polymers with significant low energy gap combining electroactivity.