Work function and negative electron affinity of ultrathin barium fluoride films

Thin films of barium fluorides with different thicknesses were deposited on GaAs substrate by electron beam evaporation. The aim of the work was to identify the best growth conditions for the production of coatings with a low work function suitable for the anode of hybrid thermionic-photovoltaic (TIPV) devices. The chemical composition and work function φ of the films with different thicknesses were investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The lowest value of φ = 2.1 eV was obtained for the film with a thickness of ~2 nm. In the valence band spectra of the films at low kinetic energy, near the cutoff, a characteristic peak of negative electron affinity was present. This effect contributed to a further reduction of the film's work function.     

Experimental and Computational Studies of the Molybdenum‐Flanking Arene Interaction in Quadruply Bonded Dimolybdenum Complexes with Terphenyl Ligands

To clarify the nature of the Mo?C_arene interaction in terphenyl complexes with quadruple Mo?Mo bonds, ether adducts of composition [Mo₂(Ar′)(I)(O₂CR)₂(OEt₂)] have been prepared and characterized (Ar′=Ar^Xyl₂, R=Me; Ar′=ArMes₂, R=Me; Ar′=Ar^Xyl2, R=CF₃) (Mes=mesityl; Xyl=2,6‐Me₂C₆H₃, from now on xylyl) and their reactivity toward different neutral Lewis bases investigated. PMe₃, P(OMe)₃ and PiPr₃ were chosen as P‐donors and the reactivity studies complemented with the use of the C‐donors CNXyl and CN₂C₂Me₄ (1,3,4,5‐tetramethylimidazol‐2‐ylidene). New compounds of general formula [Mo₂(Ar′)(I)(O₂CR)₂( L )] were obtained, except for the imidazol‐2‐ylidene ligand that yielded a salt‐like compound of composition [Mo₂(Ar^Xyl2)(O₂CMe)₂(CN₂C₂Me₄)₂]I. The Mo?C_arene interaction in these complexes has been analyzed with the aid of X‐ray data and computational studies. This interaction compensates the coordinative and electronic unsaturation of one of the Mo atoms in the above complexes, but it seems to be weak in terms of sharing of electron density between the Mo and C_arene atoms and appears to have no appreciable effect in the length of the Mo?Mo, Mo?X, and Mo? L bonds present in these molecules.     

Effects of Salts on the Micellization of a Short-Tailed Nonionic Ethoxylated Surfactant: An Intradiffusion Study

In commercial formulations, surfactants are often co-formulated with inorganic electrolytes, which are included as inexpensive thickeners. Salts affect the surfactant’s aggregative and functional behavior. However, while the electrolyte effect on the self-aggregation of ionic surfactants can be rationalized in terms of electrostatic interactions, in the case of nonionic surfactants the molecular determinants are still unclear. In this work, we investigate the effects of alkali and alkaline–earth metal chlorides on the micellization of the nonionic surfactant hexyl penta(oxyethylene) ether, C₆E₅, in aqueous solution. To this aim, the C₆E₅ intradiffusion (also named self-diffusion) coefficient in aqueous mixtures of various alkali and alkaline–earth metal chlorides was measured by pulsed gradient spin-echo NMR. The results show that all the considered electrolytes cause a decrease of the surfactant critical micellar concentration, cmc, while the micellar size is almost unaffected. The experimental evidence can be interpreted in terms of de-hydration of the apolar alkyl tails with a minor contribution arising from the dehydration of the poly(ethylene oxide) headgroups. The order of effectiveness of the different cations follows the Hofmeister series, some aspects of which are briefly discussed.     

Synthesis of 3-amino-4-fluoropyrazoles

Fluorinated pyrazoles bearing additional functional groups that allow further functionalization are of considerable interest as building blocks in medicinal chemistry. The developed synthetic strategy for new 3-amino-4-fluoropyrazoles consists of a monofluorination of β-methylthio-β-enaminoketones using 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) toward the corresponding monofluorinated enaminoketones, followed by condensation with different hydrazines.     

Amphiphilic antioxidants from "cashew nut shell liquid" (CNSL) waste

Hydrogenated cardanol and cardols, contained in industrial grade cardanol oil and obtained by distillation of the raw "cashew nut shell liquid" (CNSL), are easily transformed into efficient 4-thiaflavane antioxidants bearing a long alkyl chain on A ring and a catechol group on B ring.     

Adlayers of dimannoside thiols on gold: surface chemical analysis

Carbohydrate films on gold based on dimannoside thiols (DMT) were prepared, and a complementary surface chemical analysis was performed in detail by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), near-edge X-ray absorption fine structure (NEXAFS), FT-IR, and contact angle measurements in order to verify formation of ω-carbohydrate-functionalized alkylthiol films. XPS (C 1s, O 1s, and S 2p) reveals information on carbohydrate specific alkoxy (C-O) and acetal moieties (O-C-O) as well as thiolate species attached to gold. Angle-resolved synchrotron XPS was used for chemical speciation at ultimate surface sensitivity. Angle-resolved XPS analysis suggests the presence of an excess top layer composed of unbound sulfur components combined with alkyl moieties. Further support for DMT attachment on Au is given by ToF-SIMS and FT-IR analysis. Carbon and oxygen K-edge NEXAFS spectra were interpreted by applying the building block model supported by comparison to data of 1-undecanethiol, poly(vinyl alcohol), and polyoxymethylene. No linear dichroism effect was observed in the angle-resolved C K-edge NEXAFS.     

Environmental effects on vibrational properties of carotenoids: experiments and calculations on peridinin

Carotenoids are employed in light-harvesting complexes of dinoflagellates with the two-fold aim to extend the spectral range of the antenna and to protect it from radiation damage. We have studied the effect of the environment on the vibrational properties of the carotenoid peridinin in different solvents by means of vibrational spectroscopies and QM/MM molecular dynamics simulations. Three prototypical solvents were considered: cyclohexane (an apolar/aprotic solvent), deuterated acetonitrile (a polar/aprotic solvent) and methanol (a polar/protic solvent). Thanks to effective normal mode analysis, we were able to assign the experimental Raman and IR bands and to clarify the effect of the solvent on band shifts. In the 1500-1650 cm(-1) region, seven vibrational modes of the polyene chain were identified and assigned to specific molecular vibrations. In the 1700-1800 cm(-1) region a strong progressive down-shift of the lactonic carbonyl frequency is observed passing from cyclohexane to methanol solutions. This has been rationalized here in terms of solvent polarity and solute-solvent hydrogen bond interactions. On the basis of our data we propose a classification of non-equivalent peridinins in the Peridinin-Chlorophyll-Proteins, light-harvesting complexes of dinoflagellates.     

Surface-enhanced fluorescence and surface-enhanced Raman scattering of push–pull molecules: sulfur-functionalized 4-amino-7-nitrobenzofurazan adsorbed on Ag and Au nanostructured substrates

We investigated the chemisorption of self-assembled monolayers of sulfur-functionalized 4-amino-7-nitrobenzofurazan on gold and silver nanoisland films (NIFs) by means of surface-enhanced fluorescence (SEF) and surface-enhanced Raman scattering (SERS). The ligand is a push–pull molecule, where an intramolecular charge transfer occurs between an electron-donor and an electron-acceptor group, thus exhibiting nonlinear optical properties that are related to both SERS and SEF effects. The presence of different heteroatoms in the molecule ensures the possibility of chemical interaction with both silver and gold substrates. The SERS spectra suggest that furazan is bound to silver via lone pairs of the nitrogen atoms, whereas the ligand is linked to gold via a sulfur atom. Silver NIFs provide more efficient enhancement of both fluorescence and Raman scattering in comparison with gold NIFs. The present SEF and SERS investigation could provide useful information for foreseeing changes in the nonlinear responses of this push–pull molecule.