Small D–π–A Systems with o‐Phenylene‐Bridged Accepting Units as Active Materials for Organic Photovoltaics

Donor–acceptor (D–π–A) systems that combine triarylamine donor blocks and dicyanovinyl (DCV) acceptor groups have been synthesized. Starting from the triphenylamine (TPA)? thiophene? DCV compound ( 1 ) as a reference system, various synthetic approaches have been developed for controlling the light‐harvesting properties and energy levels of the frontier orbitals in this molecule. Thus, the introduction of methoxy groups onto TPA, the replacement of one phenyl ring of TPA by a thiophene ring, or the extension of the π‐conjugating spacer group lead to the modulation of the HOMO level. On the other hand, the fusion of the DCV group onto the vicinal thiophene ring by an ortho‐phenylene bridge allows for a specific fine‐tuning of the LUMO level. The electronic properties of the molecules were analyzed by using UV/Vis spectroscopy and cyclic voltammetry and the compounds were evaluated as donor materials in basic bilayer planar heterojunction solar cells by using C₆₀ as acceptor material. The relationships between the electronic properties of the donors and the performance of the corresponding photovoltaic devices are discussed. Bilayer planar heterojunction solar cells that used reference compound 1 and C₇₀ afforded power‐conversion efficiencies of up to 3.7 %.     

Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid‐State NMR Spectroscopies and DFT Calculations

Boronic acids (R‐B(OH)₂) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R‐B(OH)₃^?) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C₄H₉‐B(OH)₃]₂, which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid‐state NMR spectroscopy (¹H, ¹³C, ¹¹B and ⁴³Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave—GIPAW—method). These data allow relationships between the geometry around the OH groups in boronates and the IR and ¹H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic–inorganic materials containing boronate building blocks.     

Reversible Control over Molecular Recognition in Surface‐Bound Photoswitchable Hydrogen‐Bonding Receptors: Towards Read–Write–Erase Molecular Printboards

The synthesis of an anthracene‐bearing photoactive barbituric acid receptor and its subsequent grafting onto azide‐terminated alkanethiol/Au self‐assembled monolayers by using an Cu^I‐catalyzed azide–alkyne reaction is reported. Monolayer characterization using contact‐angle measurements, electrochemistry, and spectroscopic ellipsometry indicate that the monolayer conversion is fast and complete. Irradiation of the receptor leads to photodimerization of the anthracenes, which induces the open‐to‐closed gating of the receptor by blocking access to the binding site. The process is thermally reversible, and polarization‐modulated IR reflection–absorption spectroscopy indicates that photochemical closure and thermal opening of the surface‐bound receptors occur in 70 and 100 % conversion, respectively. Affinity of the open and closed surface‐bound receptor was characterized by using force spectroscopy with a barbituric‐acid‐modified atomic force microscope tip.     

Principal hierarchies of infinite-dimensional Frobenius manifolds: The extended 2D Toda lattice

We define a dispersionless tau-symmetric bihamiltonian integrable hierarchy on the space of pairs of functions analytic inside/outside the unit circle with simple poles at 0/∞$0/\infty$ respectively, which extends the dispersionless 2D Toda hierarchy of Takasaki and Takebe. Then we construct the deformed flat connection of the infinite-dimensional Frobenius manifold _M0$M_0$ introduced by Carlet, Dubrovin and Mertens (2011) [3] and, by explicitly solving the deformed flatness equations, we prove that the extended 2D Toda hierarchy coincides with principal hierarchy of _M0$M_0$.     

Synthesis of substituted 1-trifluoromethyl and 1-perfluoroalkyl-3-(arylamino)prop-2-en-1-one: advances in the mechanism of Combes 2-trifluoromethyl and 2-perfluoroalkyl quinolines synthesis

We report a new synthesis and our study of the mechanism of formation of substituted 1-trifluoromethyl and 1-perfluoroalkyl-3-(phenylamino)prop-2-en-1-one starting from 3-(R-phenoxy)-3-perfluoroalkyl-prop-2-enals and arylamines. Reactivity study of the intermediates confirmed that 3-perfluoroalkyl-N,N′-diphenyl-1,5-diazapentadienes are the synthetic intermediates of the synthesis of 2-perfluoroalkylquinolines. The mechanism of the reaction of 1-trifluoromethyl and 1-perfluoroalkyl-3-(phenylamino)prop-2-en-1-one with POCl₃ was studied. To our knowledge this is the first detection and isolation of N,N′-diaryldiazapentadiene derivatives as intermediates in the Combes F-alkyl substituted quinoline synthesis starting from enaminoketones. Finally, we succeeded isolating and identifying unsymmetrically substituted 2-perfluorolakyldiazapentadiene.     

Survey of pyrrolizidine alkaloids in teas and herbal teas on the Swiss market using HPLC-MS/MS

Pyrrolizidine alkaloids (PAs) are a large class of natural compounds amongst which the esterified 1,2-unsaturated necine base is toxic for humans and livestock. In the present study, a method was developed and validated for the screening and quantification of nine PAs and one PA N-oxide in teas (Camellia sinensis (L.) O. Kuntze) and herbal teas (camomile, fennel, linden, mint, rooibos, verbena). Samples were analysed by HPLC on a RP-column, packed with sub-2 μm core-shell particles, and quantified using tandem mass spectrometry operating in the positive electrospray ionisation mode. These PAs and some of their isomers were detected in a majority of the analysed beverages (50/70 samples). In 24 samples, PA concentrations were above the limit of quantification and the sum of the nine targeted PAs was between 0.021 and 0.954 μg per cup of tea. Thus, in some cases, total concentrations exceed the maximum daily intake recommended by the German Federal Institute for Risk Assessment and the UK’s Committee On Toxicity (i.e. 0.007 μg kg^?1 bw). Graphical Abstract

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Toward a Raman/FORS discrimination between Art Nouveau and contemporary stained glasses from CdSxSe1 − x nanoparticles signatures

CdS_xSe_{1 − x} quantum dots received considerable attention in academic studies and as cut‐off filters and indirect‐gap semiconductors. These later compounds have also been used for artistic purposes to produce colored glass since the 1920s thanks to their bright colors. Because non‐invasive conditions are now mandatory when considering objects belonging to the cultural heritage, the use of Raman and fiber optics reflectance spectroscopy has been identified as potential ones to obtain information about the nanostructure of six samples of historical glass produced between the late 1920s and modern days. The average elemental composition of the nanocrystals has been deduced processing both optical and vibrational data, and the result arising has been compared taking into account the several factors affecting the experimental results. The diffusion of zinc inside the nanocrystals has also been questioned by the shift caused on the CdS‐ and CdSe‐like phonon band wavenumber and on the absorption edge wavelength. An investigation of the size distribution and crystallinity of CdS_xSe_{1 − x} nanoparticles has been also performed considering those parameters that are mainly influenced by the disorder of the system, such as the extent of the Urbach tail and the Raman bandwidth. Thanks to the results obtained, discrimination between the more recent glass and the older Art Nouveau ones has been verified, leading to the identification of a useful analytical protocol for conservation purposes. Copyright © 2015 John Wiley & Sons, Ltd.