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A new straightforward synthetic strategy has been elaborated to achieve star-shaped triazatrinaphthylene and, for the first time, triazatrianthrylene derivatives. Their solution- and solid-state properties were thoroughly characterized by cyclic voltammetry, UV-vis absorption spectroscopy, X-ray diffraction, and density functional theory calculations. Original hexagonal molecular arrangements were found in the crystal phase, which opens a new pathway for designing materials with improved three-dimensional charge-transport properties.
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One of the biggest global challenges for our societies is to provide natural resources to the rapidly expanding population while maintaining sustainable and ecologically friendly products. The increasing public concern about toxic insecticides has resulted in the rapid development of alternative techniques based on natural infochemicals (ICs). ICs (e.g., pheromones, allelochemicals, volatile organic compounds) are secondary metabolites produced by plants and animals and used as information vectors governing their interactions. Such chemical language is the primary focus of chemical ecology, where behavior-modifying chemicals are used as tools for green pest management. The success of ecological programs highly depends on several factors, including the amount of ICs that enclose the crop, the range of their diffusion, and the uniformity of their application, which makes precise detection and quantification of ICs essential for efficient and profitable pest control. However, the sensing of such molecules remains challenging, and the number of devices able to detect ICs in air is so far limited. In this review, we will present the advances in sensing of ICs including biochemical sensors mimicking the olfactory system, chemical sensors, and sensor arrays (e-noses). We will also present several mathematical models used in integrated pest management to describe how ICs diffuse in the ambient air and how the structure of the odor plume affects the pest dynamics.
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Feromonas , Compuestos Orgánicos Volátiles , Animales , Nariz Electrónica , Odorantes , PlantasRESUMEN
Tin dioxide (SnO2) nanoparticles were straightforwardly synthesized using an easily scaled-up liquid route that involves the hydrothermal treatment, either under acidic or basic conditions, of a commercial tin dioxide particle suspension including potassium counterions. After further thermal post-treatment, the nanomaterials have been thoroughly characterized by Fourier transform infrared and Raman spectroscopy, powder X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and nitrogen sorption porosimetry. Varying pH conditions and temperature of the thermal treatment provided cassiterite SnO2 nanoparticles with crystallite sizes ranging from 7.3 to 9.7 nm and Brunauer-Emmett-Teller surface areas ranging from 61 to 106 m2·g-1, acidic conditions favoring potassium cation removal. Upon exposure to a reducing gas (H2, CO, and volatile organic compounds such as ethanol and acetone) or oxidizing gas (NO2), layers of these SnO2 nanoparticles led to highly sensitive, reversible, and reproducible responses. The sensing results were discussed in regard to the crystallite size, specific area, valence band energy, Debye length, and chemical composition. Results highlight the impact of the counterion residuals, which affect the gas-sensing performance to an extent much higher than that of size and surface area effects. Tin dioxide nanoparticles prepared under acidic conditions and calcined in air showed the best sensing performances because of lower amount of potassium cations and higher crystallinity, despite the lower surface area.
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Recent improvement in the performance of the n-type organic semiconductors as well as thin gate dielectrics based on cross-linked polymers offers new opportunities to develop high-performance low-voltage n-type OFETs suitable for organic complementary circuits. Using TIPS-tetracyanotriphenodioxazine (TIPS-TPDO-tetraCN) and cross-linked poly(methyl methacrylate) (c-PMMA), respectively as n-type organic semiconductor and gate dielectric, linear regime field-effect mobility (1.8 ± 0.2) × 10(-2) cm(2) V(-1)s(-1), small spatial standard deviation of threshold voltage (â¼0.1 V), and operating voltage less than 3 V are attainable with the same device structure and contact materials used commonly for p-type OFETs. Through comparative static and dynamic characterizations of c-PMMA and PMMA gate dielectrics, it is shown that both smaller thickness and larger relative permittivity of c-PMMA contributes to reduced operating voltage. Furthermore, negligible hysteresis brings evidence to small trap states in the semiconductor near gate dielectric of the n-type OFETs with c-PMMA. The use of TIPS-TPDO-tetraCN and c-PMMA is fully compatible with polyethylene terephthalate substrate, giving promise to various flexible applications.
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New 2-6 wt% RuO2-ZnO heterojunction nanocatalysts were synthesized by a straightforward two-step procedure. They were composed of a porous network of aggregated 25 nm wurtzite ZnO nanocrystallites modified with RuO2 and showed enhanced light absorption in the visible region due to surface plasmon resonance. In order to investigate the energetic structure of the photocatalyst XPS core line and valence band spectra of in situ in UHV prepared heterointerfaces were compared to results obtained from the particles. The shift of Zn 2p3/2 and O 1s core level spectra was determined to be at least 0.80 ± 0.05 eV for the in situ prepared heterojunction whereas it was found to be 0.40 ± 0.05 and 0.45 ± 0.05 eV, respectively, in the photocatalysts. The different values were ascribed to the reduced size of the particles and the different measurability of band bending at the interface of the heterojunction RuO2-ZnO compared to the nanoparticles. The RuO2/ZnO photocatalysts showed higher photocatalytic activity and recyclability than pure ZnO for the degradation of various dyes under UV light irradiation due to vectorial charge separation of photogenerated electrons and holes resulting from internal electric field, the ruthenium oxide acting as a quasi-metallic contact.
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New π-conjugated structures are constantly the subject of research in dyes and pigments industry and electronic organic field. In this context, the triphenodioxazine (TPDO) core has often been used as efficient photostable pigments and once integrated in air stable n-type organic field-effect transistor (OFET). However, little attention has been paid to the TPDO core as soluble materials for optoelectronic devices, possibly due to the harsh synthetic conditions and the insolubility of many compounds. To benefit from the photostability of TPDO in dye-sensitized solar cells (DSCs), an original synthetic pathway has been established to provide soluble and dissymmetric molecules applied to a suitable design for the sensitizers of DSC. The study has been pursued by the theoretical modeling of opto-electronic properties, the optical and electronic characterizations of dyes and elaboration of efficient devices. The discovery of new synthetic pathways opens the way to innovative designs of TPDO for materials used in organic electronics.
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Nanoporous SnO(2)-ZnO heterojunction nanocatalyst was prepared by a straightforward two-step procedure involving, first, the synthesis of nanosized SnO(2) particles by homogeneous precipitation combined with a hydrothermal treatment and, second, the reaction of the as-prepared SnO(2) particles with zinc acetate followed by calcination at 500 °C. The resulting nanocatalysts were characterized by X-ray diffraction (XRD), FTIR, Raman, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption analyses, transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectroscopy. The SnO(2)-ZnO photocatalyst was made of a mesoporous network of aggregated wurtzite ZnO and cassiterite SnO(2) nanocrystallites, the size of which was estimated to be 27 and 4.5 nm, respectively, after calcination. According to UV-visible diffuse reflectance spectroscopy, the evident energy band gap value of the SnO(2)-ZnO photocatalyst was estimated to be 3.23 eV to be compared with those of pure SnO(2), that is, 3.7 eV, and ZnO, that is, 3.2 eV, analogues. The energy band diagram of the SnO(2)-ZnO heterostructure was directly determined by combining XPS and the energy band gap values. The valence band and conduction band offsets were calculated to be 0.70 ± 0.05 eV and 0.20 ± 0.05 eV, respectively, which revealed a type-II band alignment. Moreover, the heterostructure SnO(2)-ZnO photocatalyst showed much higher photocatalytic activities for the degradation of methylene blue than those of individual SnO(2) and ZnO nanomaterials. This behavior was rationalized in terms of better charge separation and the suppression of charge recombination in the SnO(2)-ZnO photocatalyst because of the energy difference between the conduction band edges of SnO(2) and ZnO as evidenced by the band alignment determination. Finally, this mesoporous SnO(2)-ZnO heterojunction nanocatalyst was stable and could be easily recycled several times opening new avenues for potential industrial applications.
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Azul de Metileno/química , Nanoestructuras/química , Compuestos de Estaño/química , Óxido de Zinc/química , Catálisis , Tamaño de la Partícula , Procesos Fotoquímicos , Propiedades de Superficie , Compuestos de Estaño/síntesis química , Óxido de Zinc/síntesis químicaRESUMEN
Connection of SnO2 particles by simple UV irradiation in air yielded cassiterite SnO2 porous films at low temperature. XPS, FTIR, and TGA-MS data revealed that the UV treatment has actually removed most of the organics present in the precursor SnO2 colloid and gave more hydroxylated materials than calcination at high temperature. As electrodes for dye-sensitized solar cells (DSCs), the N3-modified 1-5 µm thick SnO2 films showed excellent photovoltaic responses with overall power conversion efficiency reaching 2.27% under AM1.5G illumination (100 mW cm⻲). These performances outperformed those of similar layers calcined at 450 °C mostly due to higher V(oc) and FF. These findings were rationalized in terms of slower recombination rates for the UV-processed films on the basis of dark current analysis, photovoltage decay, and electrical impedance spectroscopy studies.
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We show by means of STM that C(60) molecules can be trapped into specific sites of a 2D double-cavity open network, thus forming long-range alignments of single molecules. Since only one of the two cavities has the right size to host C(60), the smallest cavity remains empty and is thus available to trap additional species of smaller size. This novel 2D supramolecular network opens new perspectives in the design of multicomponent guest-host architectures with electronic functionalities.
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Quaterthiophenes 4T, Oct-4T, and Tol-4T based on a central 2,2'-bithiophene core alpha,omega-terminated with 4,4-unsubstituted and 4,4-disubstituted n-octyl or p-tolyl indeno[1,2-b]thiophene have been synthesized by Stille or Miyaura-Suzuki couplings. Compound 4T was also synthesized by an alternative route involving a soluble precursor bearing solubilizing trimethylsilyl groups which have been eliminated in the last step. The electronic properties of the compounds have been analyzed by cyclic voltammetry, UV-vis absorption and fluorescence emission spectroscopy. Thermal evaporation of 4T and Oct-4T leads to crystalline thin films and UV-vis absorption and X-ray diffraction data for these films suggest that the molecules adopt a quasi-vertical orientation onto the substrate. Strong pi-pi intermolecular interactions have been observed for 4T but not for molecules Oct-4T due to the presence of n-octyl chains. Sublimed thin films of Tol-4T show an amorphous character. The characterization of field-effect transistors fabricated from these three materials gave a hole-mobility of 2.2 x 10(-2) cm2 V(-1) s(-1) with an on/off ratio of 2.2 x 10(4) for 4T while no field-effect was observed for Oct-4T and Tol-4T.
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Six anthraquinone derivatives were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF MS). Clear (pseudo) molecular ions were observed for all the compounds. Interestingly, for some derivatives, strong ions with double cation adduction were also recorded in the positive mode. It is remarkable that all these ions are singly charged. In this work, possible mechanisms for the double cation adduction were investigated and discussed. It appears that the double cation adduction was due to the electron deficient nature of the derivatives, and formed by taking up two singly charged cations and one electron. Substituents on the anthraquinone ring were found to have a significant effect on the double cation adduction. In contrast, no considerable influence of the acidity of MALDI matrix/solution was observed, even on the double proton adduction. Furthermore, it was demonstrated that double cation adduction might occur in the MALDI gas-phase plume. In addition to the anthraquinones, three more electron deficient compounds of different types, i.e. a perylene bisimide derivative (PB), 3,7-decanoylamino-4,8-dihydrobenzo[1,2-b:4,5-b']dithiophene-4,8-dione (TQ) and 6,6-phenyl C61-butyric acid methyl ester (PCBM), were also analyzed with MALDI TOF MS. The results indicate that the 'abnormal' double cation adduction might be a 'normal' phenomenon in the MALDI TOF MS analysis of many electron deficient compounds.
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An acene fused-thiophene hybrid p-semiconductor exhibiting high thermal stability has been synthesized via a soluble precursor bearing sterically interacting trimethylsilyl groups. [structure: see text]
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[structure: see text] Planarized star-shaped oligothiophenes 1 have been synthesized by connecting short-chain oligothiophenes on a benzo[1,2-b:3,4-b':5,6-b' ']trithiophene central core. Their electrochemical and optical properties have been characterized by cyclic voltammetry and UV-visible spectroscopy, respectively. These results associated with theoretical calculations show the advantage of benzotrithiophene as a central core in terms of pi-electron delocalization.
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A set of twelve porphyrin dimers has been prepared to give information on how the type of connectivity between a porphyrin core and a bridge can influence the interporphyrin electronic interaction. The new porphyrin systems are substituted directly at the meso position with an oligothiophene chain tethered either with a single C-C sigma bond, a trans ethylenyl group, or a acetylenyl group. The compounds are easily obtained by palladium-catalyzed cross-coupling reactions (Stille, Heck, and Sonogashira) between 5-iodo-10,15,20-(3,5-ditert-butylphenyl)porphyrin and the appropriate oligothiophene derivative. This synthetic approach is straightforward and very effective for preparing oligothiophene-based prophyrin systems. The absorption spectra and the fluorescence properties of the dimers demonstrated the crucial importance of the characteristics of the chemical bond used to connect the bridge to the porphyrin unit. The magnitude of the electronic communication can thus be significantly modulated by altering the type of bond connectivity used to link the chromophore to the bridge. The present work shows that an oligothiophene spacer is a viable class of linker for connecting porphyrins, and that a quaterthiophene appended with ethynyl linkages affords a high electronic interaction over a distance as large as 28 A. A detailed computational study of these dimers has clarified the conditions needed for a conjugated system to behave as a molecular wire. These conditions are full planarity of the molecule and proper energy matching between the frontier orbitals of the bridge and the porphyrin. Intermolecular energy transfer in asymmetrical dyads composed of a zinc porphyrin and a freebase porphyrin has been studied by fluorescence spectroscopy. In all systems, this process is more than 98% efficient, and its rate constant decreases steadily in the order 4ZH > 1ZH > 3ZH approximately 2ZH. Thus, the largest rate (kEnT = 1.2 x 10(11) s-1) was found in the dyad linked with bisethynyl quaterthiophene, which represents the longest bridge within the series. These results clearly demonstrate that strong communication and also efficient photoinduced processes can be promoted over a large distance if the electronic structure of the molecular connector is appropriately chosen.
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[reaction: see text] An unsymmetrical analogue of 3,4-ethylenedioxythiophene (EDOT) has been synthesized by transetherification of 3,4-dimethoxythiophene. Electropolymerization leads to a stable electroactive polymer with electrochemical and electronic properties intermediate between those of the two symmetrical parent polymers poly(EDOT) and poly(3,4-ethylenedithiathiophene). Experimental work shows that the 2- and 5-positions possess a different reactivity, thus opening the possibility of synthesizing regioregular oligomers or polymers.