A Bioinspired Molybdenum Complex as a Catalyst for the Photo‐ and Electroreduction of Protons

A molybdenum–dithiolene–oxo complex was prepared as a model of some active sites of Mo/W‐dependent enzymes. The ligand, a quinoxaline–pyran‐fused dithiolene, mimics molybdopterin present in these active sites. For the first time, this type of complex was shown to be active as a catalyst for the photoreduction of protons with excellent turnover numbers (500) and good stability in aqueous/organic media and for the electroreduction of protons in acetonitrile with remarkable rate constants (1030 s^?1 at ?1.3 V versus Ag/AgCl). DFT calculations provided insight into the catalytic cycle of the reaction, suggesting that the oxo ligand plays a key role in proton exchange. These results provide a basis to optimize this new class of H₂‐evolving catalysts.     

Validating DEA as a ranking tool: An application of DEA to assess performance in higher education

There is a general interest in ranking schemes applied to complex entities described by multiple attributes. Published rankings for universities are in great demand but are also highly controversial. We compare two classification and ranking schemes involving universities; one from a published report, ‘Top American Research Universities’ by the University of Florida's TheCenter and the other using DEA. Both approaches use the same data and model. We compare the two methods and discover important equivalences. We conclude that the critical aspect in classification and ranking is the model. This suggests that DEA is a suitable tool for these types of studies.     

Characterization of acid-base properties of polymers and other materials: relevance to adhesion science and technology

This paper reviews the background to the theory of Lewis acid-base (AB) interactions in adhesion, adsorption, wetting and mixing of polymers and other materials (pigments, fillers, fibres, etc.). These specific materials interactions require the revision of old concepts («polar» interactions) and the development of new analytical techniques and methodologies. Four of the most currently used techniques to characterize AB interactions are described: contact angle measurements, inverse gas chromatography. X-ray photoelectron spectroscopy, and atomic force microscopy.     

Variability of two essential oils of Kundmannia sicula (L.) DC., a traditional Algerian medicinal plant

The essential oils of the aerial parts of Kundmannia sicula (L.) DC collected from two Algerian localities, El Kala (near the coast) and Béjaia (from a meadow about 10 km from the coast), were analysed by GC and GC-MS. Although both samples showed similar overall chemical compositions, the major components of the Béjaia sample were identified as being spathulenol (14.8%), caryophyllene oxide (12.2%), salvial-4(14)en-1-one (10.1%), 1,5-epoxysalvial-4(14)ene (5.2%) and germacrene D (3.2%), while in the ElKala sample the main compounds were found to be salvial-4(14)en-1-one (16.4%), 1,5-epoxysalvial-4(14)ene (6.5%), chrysanthenyl acetate (5.2%) and alpha-amorphene (2.9%).     

Chemical Composition Profiling and Antifungal Activity of Saffron Petal Extract

Numerous fungal plant pathogens can infect fresh fruits and vegetables during transit and storage conditions. The resulting infections were mainly controlled by synthetic fungicides, but their application has many drawbacks associated with the threatened environment and human health. Therefore, the use of natural plants with antimicrobial potential could be a promising alternative to overcome the side effects of fungicides. In this regard, this study aimed at evaluating the antifungal activity potential of saffron petal extract (SPE) against three mains important fungal pathogens: Rhizopus stolonifer, Penicillium digitatum and Botritys cinerea, which cause rot decay on the tomato, orange and apple fruits, respectively. In addition, the organic composition of SPE was characterized by attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopy and its biochemical, and gas chromatography-mass spectrometry (GC-MS) analyses were carried out. The obtained results highlighted an increased inhibition rate of the mycelial growth and spore germination of the three pathogenic fungi with increasing SPE concentrations. The mycelial growth and spore germination were completely inhibited at 10% of the SPE for Rhizopus stolonifer and Penicillium digitatum and at 5% for B. cinerea. Interestingly, the in vivo test showed the complete suppression of Rhizopus rot by the SPE at 10%, and a significant reduction of the severity of grey mold disease (37.19%) and green mold, when applied at 5 and 10%, respectively. The FT-IR spectra showed characteristic peaks and a variety of functional groups, which confirmed that SPE contains phenolic and flavonoid components. In addition, The average value of the total phenolic content, flavonoid content and half-maximal inhibitory concentration (IC₅₀) were 3.09 ± 0.012 mg GAE/g DW, 0.92 ± 0.004 mg QE/g DW and 235.15 ± 2.12 µg/mL, respectively. A volatile analysis showed that the most dominant component in the saffron petal is 2(5H)-Furanone (92.10%). Taken together, it was concluded that SPE could be used as an alternative to antioxidant and antifungal compounds for the control of postharvest diseases in fruits.     

Photomagnetic effect in a cyanide-bridged mixed-valence {Fe(II)2Fe(III)2} molecular square

The self-assembly of [Fe(III)(Tp)(CN)(3)](-) and [Fe(II)(bik)(2)(S)(2)](2+) affords the cyanide-bridged mixed valence {Fe(III)(2)Fe(II)(2)}(2+) molecular square, which exhibits a photomagnetic effect under laser light irradiation at low temperature and also shows thermal spin-state conversion near ambient temperature.     

Metal–organic interaction probed by First Principles STM simulations

The Review is devoted to recent progress made from the combination of Scanning Tunneling Microscope (STM) experiments and First Principles atomistic simulations in the chemical characterization of metal–organic interfaces. Density Functional Theory (DFT) has now reached the point to mimic in a quantitative way two pillars of the STM probe: the imaging mode convoluting the topographic and electronic properties and the spectroscopy modes comprising of elastic and inelastic detection ways. We present a selection of hybrid interfaces ranging from isolated benzene derivatives to thin honeycomb carbon film – a single graphene layer – deposited onto transition metal surfaces. The direct experimental analysis of these interfaces was error-prone, necessitating the confrontation with First Principles atomistic simulations. The few examples thus illustrate the power of different kinds of STM simulations to complement the STM data, in order to unambiguously identify the chemical structure of organic adsorbates.     

Thermodynamic Investigation of the Micellization and the Adsorption of Short Perfluoroalkylated Diols via Fluorescence Spectroscopy and Tensiometry

The micellization and adsorption of two short chain perfluorodiols 3,3,4,4,5,5,6,6,6-nonafluorohexane-1,2-diol (nFHD) and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1,2-diol (tFOD) are examined from a thermodynamic point of view as a function of temperature and methanol content. The microenvironment of the fluorinated aggregates is evaluated by the fluorescence probe method using pyrene and a molecular rotor 1,1-dicyano-4-p-dimethylaminophenyl)-1,3-butadiene (DMAPhC). The formation of micellar aggregates being evidenced, the results are discussed in terms of the polarity and of the cohesion behavior of the micellar aggregates by taking into account the methanol (MeOH) effect. The critical micellization concentrations thus determined are compared with those given by surface tension measurements. Micellar and adsorption thermodynamic parameters such as Gibbs free energies, enthalpies, and entropies are determined together with the surface areas. The results are compared with literature data and discussed. A model for describing the adsorption process of the fluorinated compounds upon the influence of methanol is finally proposed. Copyright 2001 Academic Press.     

Determination of traces of As,Cd, Cr,Hg, Mn,Ni, Sb,Se, Sn and Pb in human hair by triple quadrupole ICP-MS

With the wide range of metallic contaminants discharged in the environment, studying the human health requires a growing number of elements to be monitored in biological samples. Hair analysis has been suggested as a suitable tool for biomonitoring environmental and occupational exposure to toxic elements. This study describes a method for the determination of 10 trace elements in hair samples using ICP-QQQ-MS. Combining the power of the MS/MS high-energy Helium mode with the MS/MS O₂ mass-shift mode, the method offers great analytical performances with detection limits reaching 0.0014 µg g^?1 for As, 0.0016 µg g^?1 for Cd, 0.012 µg g^?1 for Cr, 0.0035 µg g^?1 for Hg, 0.0055 µg g^?1 for Mn, 0.10 µg g^?1 for Ni, 0.0012 µg g^?1 for Sb, 0.0083 µg g^?1 for Sn, 0.011 µg g^?1 for Se and Pb. The accuracy of the method was tested on a human hair ERM® certified reference material. Percent recoveries varied from 91.3% and 106.9% being always in the acceptance range of 90–110%. For all analysed elements, RSD% of repeatability ranged between 0.6% and 9.0% and those of intermediate precision did not exceed the limit of 20% being always lower than 10% (except for As). The proposed method was applied for the determination of trace elements in hair samples from 20 unexposed subjects. The geometric mean levels were as follows: Cr 0.28 µg g^?1, Mn 0.30 µg g^?1, Sn 1.04µg g^?1, Sb 0.07 µg g^?1, Hg 0.42 µg g^?1, As 0.02 µg g^?1, Cd 0.03 µg g^?1, Ni 0.51 µg g^?1, Se 0.45 µg g^?1 and Pb 1.83 µg g^?1. Element concentrations were in the same range with the reported data. The reported results may be useful for environmental exposure assessment or comparisons studies when establishing reference values of trace elements in exposed population.     

In-Situ Growth of Gadolinium Phthalocyaninato Sandwich Complexes on the Ag(111) Surface

We report a low-temperature scanning tunneling microscopy investigation of the in-situ growth of gadolinium phthalocyaninato complexes by combined deposition of free-base phthalocyanines and gadolinium atoms on a smooth Ag(111) substrate. A careful control of the stoichiometry allows the expression of a multilevel structurecomposed of irregularly distributed Gd_x-1(Pc)_x complexes, x=2–5, thus paving new avenues for surface-confined columnar growth.