Thin Polymer Films by Oxidative or Reductive Electropolymerization and Their Application in Electrochromic Windows and Thin-Film Sensors.

Electrically conducting and semiconducting polymers represent a special and still very attractive class of functional chromophores, especially due to their unique optical and electronic properties and their broad device application potential. They are potentially suitable as materials for several applications of high future relevance, for example flexible photovoltaic modules, components of displays/screens and batteries, electrochromic windows, or photocatalysts. Therefore, their synthesis and structure elucidation are still intensely investigated. This article will demonstrate the very fruitful interplay of current electropolymerization research and its exploitation for science education issues. Experiments involving the synthesis of conducting polymers and their assembly into functional devices can be used to teach basic chemical and physical principles as well as to motivate students for an innovative and interdisciplinary field of chemistry.

Croton lechleri Extracts as Green Corrosion Inhibitors of Admiralty Brass in Hydrochloric Acid.

Croton lechleri, commonly known as Dragon's blood, is a tree cultivated in the northwest Amazon rainforest of Ecuador and Peru. This tree produces a deep red latex which is composed of different natural products such as phenolic compounds, alkaloids, and others. The chemical structures of these natural products found in C. lechleri latex are promising corrosion inhibitors of admiralty brass (AB), due to the number of heteroatoms and π structures. In this work, three different extracts of C. lechleri latex were obtained, characterized phytochemically, and employed as novel green corrosion inhibitors of AB. The corrosion inhibition efficiency (IE%) was determined in an aqueous 0.5 M HCl solution by potentiodynamic polarization (Tafel plots) and electrochemical impedance spectroscopy, measuring current density and charge transfer resistance, respectively. In addition, surface characterization of AB was performed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy techniques. Chloroform alkaloid-rich extracts resulted in IE% of 57% at 50 ppm, attributed to the formation of a layer of organic compounds on the AB surface that hindered the dezincification process. The formulation of corrosion inhibitors from C. lechleri latex allows for the valorization of non-edible natural sources and the diversification of the offer of green corrosion inhibitors for the chemical treatment of heat exchangers.

Microbiologically Induced Carbonate Precipitation in the Restoration and Conservation of Cultural Heritage Materials.

Microbiologically induced carbonate precipitation (MICP) is a well-known biogeochemical process that allows the formation of calcium carbonate deposits in the extracellular environment. The high concentration of carbonate and calcium ions on the bacterial surface, which serves as nucleation sites, promotes the calcium carbonate precipitation filling and binding deteriorated materials. Historic buildings and artwork, especially those present in open sites, are susceptible to enhanced weathering resulting from environmental agents, interaction with physical-chemical pollutants, and living organisms, among others. In this work, some published variations of a novel and ecological surface treatment of heritage structures based on MICP are presented and compared. This method has shown to be successful as a restoration, consolidation, and conservation tool for improvement of mechanical properties and prevention of unwanted gas and fluid migration from historical materials. The treatment has revealed best results on porous media matrixes; nevertheless, it can also be applied on soil, marble, concrete, clay, rocks, and limestone. MICP is proposed as a potentially safe and powerful procedure for efficient conservation of worldwide heritage structures.

Microporous Polymer-Modified Glassy Carbon Electrodes for the Electrochemical Detection of Metronidazole: Experimental and Theoretical Insights.

The persistence and potential toxicity of emergent pollutants pose significant threats to biodiversity and human health, emphasizing the need for sensors capable of detecting these pollutants at extremely low concentrations before treatment. This study focuses on the development of glassy carbon electrodes (GCEs) modified by films of poly-tris(4-(4-(carbazol-9-yl)phenyl)silanol (PTPTCzSiOH), poly-4,4'-Di(carbazol-9-yl)-1,1'-biphenyl (PCBP), and poly-1,3,5-tri(carbazol-9-yl)benzene (PTCB) for the detection of metronidazole (MNZ) in aqueous media. The films were characterized using electrochemical, microscopy, and spectroscopy techniques, including scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Monomers were electropolymerized through cyclic voltammetry and chronoamperometry techniques. Computational methods at the B3LYP/def2-TZVP level were employed to investigate the structural and electrochemical properties of the monomers. The electrochemical detection of MNZ utilized the linear sweep voltammetry technique. Surface characterization through SEM and XPS confirmed the proper electrodeposition of polymer films. Notably, MPN-GCEs exhibited higher detection signals compared to bare GCEs up to 3.6 times in the case of PTPTCzSiOH-GCEs. This theoretical study provides insights into the structural, chemical, and electronic properties of the polymers. The findings suggest that polymer-modified GCEs hold promise as candidates for the development of electrochemical sensors.

Recent Advances in Hole-Transporting Layers for Organic Solar Cells.

Global energy demand is increasing; thus, emerging renewable energy sources, such as organic solar cells (OSCs), are fundamental to mitigate the negative effects of fuel consumption. Within OSC's advancements, the development of efficient and stable interface materials is essential to achieve high performance, long-term stability, low costs, and broader applicability. Inorganic and nanocarbon-based materials show a suitable work function, tunable optical/electronic properties, stability to the presence of moisture, and facile solution processing, while organic conducting polymers and small molecules have some advantages such as fast and low-cost production, solution process, low energy payback time, light weight, and less adverse environmental impact, making them attractive as hole transporting layers (HTLs) for OSCs. This review looked at the recent progress in metal oxides, metal sulfides, nanocarbon materials, conducting polymers, and small organic molecules as HTLs in OSCs over the past five years. The endeavors in research and technology have optimized the preparation and deposition methods of HTLs. Strategies of doping, composite/hybrid formation, and modifications have also tuned the optical/electrical properties of these materials as HTLs to obtain efficient and stable OSCs. We highlighted the impact of structure, composition, and processing conditions of inorganic and organic materials as HTLs in conventional and inverted OSCs.

Electrochemical Sensors Based on Conducting Polymers for the Aqueous Detection of Biologically Relevant Molecules.

Electrochemical sensors appear as low-cost, rapid, easy to use, and in situ devices for determination of diverse analytes in a liquid solution. In that context, conducting polymers are much-explored sensor building materials because of their semiconductivity, structural versatility, multiple synthetic pathways, and stability in environmental conditions. In this state-of-the-art review, synthetic processes, morphological characterization, and nanostructure formation are analyzed for relevant literature about electrochemical sensors based on conducting polymers for the determination of molecules that (i) have a fundamental role in the human body function regulation, and (ii) are considered as water emergent pollutants. Special focus is put on the different types of micro- and nanostructures generated for the polymer itself or the combination with different materials in a composite, and how the rough morphology of the conducting polymers based electrochemical sensors affect their limit of detection. Polypyrroles, polyanilines, and polythiophenes appear as the most recurrent conducting polymers for the construction of electrochemical sensors. These conducting polymers are usually built starting from bifunctional precursor monomers resulting in linear and branched polymer structures; however, opportunities for sensitivity enhancement in electrochemical sensors have been recently reported by using conjugated microporous polymers synthesized from multifunctional monomers.

Thin Functional Polymer Films by Electropolymerization.

Intrinsically conducting polymers (ICPs) have been widely utilized in organic electronics, actuators, electrochromic devices, and sensors. Many potential applications demand the formation of thin polymer films, which can be generated by electrochemical polymerization. Electrochemical methods are quite powerful and versatile and can be utilized for investigation of ICPs, both for educational purposes and materials chemistry research. In this study, we show that potentiodynamic and potentiostatic techniques can be utilized for generating and characterizing thin polymer films under the context of educational chemistry research and state-of-the-art polymer research. First, two well-known bifunctional monomers (with only two linking sites)-aniline and bithiophene-and their respective ICPs-polyaniline (PANI) and polybithiophene (PBTh)-were electrochemically generated and characterized. Tests with simple electrochromic devices based on PANI and PBTh were carried out at different doping levels, where changes in the UV-VIS absorption spectra and color were ascribed to changes in the polymer structures. These experiments may attract students' interest in the electrochemical polymerization of ICPs as doping/dedoping processes can be easily understood from observable color changes to the naked eye, as shown for the two polymers. Second, two new carbazole-based multifunctional monomers (with three or more linking sites)-tris(4-(carbazol-9-yl)phenyl)silanol (TPTCzSiOH) and tris(3,5-di(carbazol-9-yl)phenyl)silanol (TPHxCzSiOH)-were synthesized to produce thin films of cross-linked polymer networks by electropolymerization. These thin polymer films were characterized by electrochemical quartz crystal microbalance (EQCM) experiments and nitrogen sorption, and the results showed a microporous nature with high specific surface areas up to 930 m2g-1. PTPHxCzSiOH-modified glassy carbon electrodes showed an enhanced electrochemical response to nitrobenzene as prototypical nitroaromatic compound compared to unmodified glassy carbon electrodes.

Highly sensitive gas-phase explosive detection by luminescent microporous polymer networks.

We propose microporous networks (MPNs) of a light emitting spiro-carbazole based polymer (PSpCz) as luminescent sensor for nitro-aromatic compounds. The MPNs used in this study can be easily synthesized on arbitrarily sized/shaped substrates by simple and low-cost electrochemical deposition. The resulting MPN afford an extremely high specific surface area of 1300 m(2)/g, more than three orders of magnitude higher than that of the thin films of the respective monomer. We demonstrate, that the luminescence of PSpCz is selectively quenched by nitro-aromatic analytes, e.g. nitrobenzene, 2,4-DNT and TNT. In striking contrast to a control sample based on non-porous spiro-carbazole, which does not show any luminescence quenching upon exposure to TNT at levels of 3 ppm and below, the microporous PSpCz shows a clearly detectable response even at TNT concentrations as low as 5 ppb, clearly demonstrating the advantage of microporous films as luminescent sensors for traces of explosive analytes. This level states the vapor pressure of TNT at room temperature.

Electrogenerated thin films of microporous polymer networks with remarkably increased electrochemical response to nitroaromatic analytes.

Thin films of microporous polymer networks (MPNs) have been generated by electrochemical polymerization of a series of multifunctional carbazole-based monomers. The microporous films show high Brunauer-Emmett-Teller (BET) surface areas up to 1300 m2 g(-1) as directly measured by krypton sorption experiments. A correlation between the number of polymerizable carbazole units of the monomer and the resulting surface area is observed. Electrochemical sensing experiments with 1,3,5-trinitrobenzene as prototypical nitroaromatic analyte demonstrate an up to 180 times increased current response of MPN-modified glassy carbon electrodes in relation to the nonmodified electrode. The phenomenon probably involves intermolecular interactions between the electron-poor nitroaromatic analytes and the electron-rich, high surface area microporous deposits, with the electrochemical reduction at the MPN-modified electrodes being an adsorption-controlled process for low scan rates. We expect a high application potential of such MPN-modified electrodes for boosting the sensitivity of electrochemical sensor devices.