New perspectives in hydrogenase direct electrochemistry

Electrochemical studies of hydrogenases, the biological catalysts of H₂ oxidation and production, have proven wrong the old saying that enzymes do not easily transfer electrons to electrodes in the absence of mediators. Many distinct hydrogenases have actually been directly connected to electrodes or particles, for studying their catalytic mechanism or for designing solar-fuels catalysts. In this review, we list the electrodes that have proved successful for direct electron transfer to hydrogenases, and we discuss recent results which illustrate new directions in this research field: the study of the biosynthesis of FeFe hydrogenase, the electrochemical characterization of non-standard NiFe or FeFe hydrogenases, the general discussion of what makes a catalyst better in one particular direction of the reaction, and the elucidation of the molecular mechanisms of hydrogenase catalysis by combining electrochemistry and theoretical chemistry, spectroscopy or photochemistry. The electrochemical methods described herein will probably prove useful for studying or using other redox enzymes.     

Untargeted metabolomic analysis using liquid chromatography quadrupole time-of-flight mass spectrometry for non-volatile profiling of wines

The current study presents a method for comprehensive untargeted metabolomic fingerprinting of the non-volatile profile of the Graciano Vitis vinifera wine variety, using liquid chromatography/electrospray ionization time of flight mass spectrometry (LC–ESI-QTOF). Pre-treatment of samples, chromatographic columns, mobile phases, elution gradients and ionization sources, were evaluated for the extraction of the maximum number of metabolites in red wine. Putative compounds were extracted from the raw data using the extraction algorithm, molecular feature extractor (MFE). For the metabolite identification the WinMet database was designed based on electronic databases and literature research and includes only the putative metabolites reported to be present in oenological matrices. The results from WinMet were compared with those in the METLIN database to evaluate how much the databases overlap for performing identifications. The reproducibility of the analysis was assessed using manual processing following replicate injections of Vitis vinifera cv. Graciano wine spiked with external standards. In the present work, 411 different metabolites in Graciano Vitis vinifera red wine were identified, including primary wine metabolites such as sugars (4%), amino acids (23%), biogenic amines (4%), fatty acids (2%), and organic acids (32%) and secondary metabolites such as phenols (27%) and esters (8%). Significant differences between varieties Tempranillo and Graciano were related to the presence of fifteen specific compounds.     

Photosensitive azobispyridine gold(I) and silver(I) complexes

The neutral and cationic dinuclear gold(I) compounds [(μ-N-N)(AuR)(2)] (N-N = 2,2'-azobispyridine (2-abpy), 4,4'-azobispyridine (4-abpy); R = C(6)F(5), C(6)F(4)OC(12)H(25)-p, C(6)F(4)OCH(2)C(6)H(4)OC(12)H(25)-p) and [(μ-N-N){Au(PR(3))}(2)](CF(3)SO(3))(2) (N-N = 2-abpy, 4-abpy, R = Ph, Me) have been obtained by displacement of a weakly coordinated ligand by an azobispyridine ligand. The corresponding silver(I) dinuclear [(μ-2-abpy){Ag(CF(3)SO(3))(PPh(3))}(2)] and polynuclear [{Ag(CF(3)SO(3))(4-abpy)}(n)] compounds have been obtained. The molecular structures of [(μ-2-abpy){Au(PPh(3))}(2)](CF(3)SO(3))(2) and [(μ-4-abpy){Au(PMe(3))}(2)](CF(3)SO(3))(2) have been confirmed by X-ray diffraction studies and feature linear gold(I) centers coordinated by pyridyl groups, and non-coordinated azo groups. In contrast the X-ray structure of [(2-abpy){Ag(CF(3)SO(3))(PPh(3))}(2)] shows tetracoordinated silver(I) centers involving chelating N-N coordination by pyridyl and azo nitrogen atoms. The gold(I) compounds with a long alkoxy chain do not behave as liquid crystals, and decompose before their melting point. The soluble gold(I) derivatives are photosensitive in solution and isomerize to the cis azo isomer under UV irradiation, returning photochemically or thermally to the most stable initial trans isomer. The silver(I) derivative [(2-abpy){Ag(CF(3)SO(3))(PPh(3))}(2)] also photoisomerizes in solution under UV irradiation, showing that its solid state structure, which would block isomerization by azo coordination, is easily broken. These processes have been monitored by UV-vis absorption and (1)H NMR spectroscopy. All these compounds are non-emissive in the solid state, even at 77 K.     

A simple acoustic model to characterize the internal low frequency sound field in centrifugal pumps

Conventional centrifugal pumps with volute casing generate fluid-dynamic noise particularly at the so-called blade-passing frequency, which is attributed to the interaction of the flow exiting the pump impeller with the volute tongue. Following previous work by the authors to characterize the effect of that blade–tongue interaction on the tonal sound produced, this paper presents a simple acoustic model for centrifugal pumps that considers ideal sound sources of arbitrary position and properties. The model is to be implemented in a software code that applies it systematically to a pump previously tested at laboratory, until identifying the set of ideal sources that best reproduce the pressure fluctuation measurements. In this model, the ideal sources are assumed to radiate plane sound waves along the impeller channels, volute, and outlet diffuser. The volute was considered to be composed by a succession of slices, each of them equivalent to a linear 3-port acoustic system with individual sound transmission and reflection coefficients. A series of tests was conducted to check the validity of the acoustic model, by applying an external acoustic load onto the pump outlet duct and measuring the noise reflected. The resulting reflection coefficient was in good agreement with the predictions of the acoustic model. Finally, the model was used to investigate the pump internal sound field at the blade-passing frequency when operating at 70% of nominal flow rate. It was concluded that the sound field can be characterized reasonably by a dipole-like source located at the tongue region.     

Algorithms for the integration and derivation of Chebyshev series

General formulas for the mth integral and derivative of a Chebyshev polynomial of the first or second kind are presented. The result is expressed as a finite series of the same kind of Chebyshev polynomials. These formulas permit to accelerate the determination of such integrals or derivatives. Besides, it is presented formulas for the mth integral and derivative of finite Chebyshev series and a numerical algorithm for the direct evaluation of the mth derivative of such a series.     

A mechanism explaining the metamorphoses of KAM islands in nonhyperbolic chaotic scattering

Nonlinear Dynamics - In the context of nonhyperbolic chaotic scattering, it has been shown that the evolution of the KAM islands exhibits four abrupt metamorphoses that strongly affect the...     

A selective supramolecular photochemical sensor for dopamine

Dopamine (DA) is an important biomarker for diseases and biological disorders. Existing techniques for DA detection suffer from drawbacks including low sensitivity and selectivity as well as interfering signals from non-target molecules. A simple and selective photochemical sensor for the determination of DA in a supramolecular manner is presented. This approach utilises the complexation properties of a highly fluorescent water-soluble complex of perylene bis(diimide) dye with the macrocyclic host cucurbit[8]uril. The method can be used for the determination of DA in aqueous media, with detection limits below 2 × 10^? 5 M, even in the presence of known interferents including ascorbic acid and the catecholamines epinephrine and norepinepherine.     

Study of ancient Islamic gilded pieces combining PIXE-RBS on external microprobe with sem images

Numerous metallic objects with very aesthetic and technological qualities have been recovered by archaeological excavations. Adequate processes of restoration and conservation treatments require the accurate determination of the elemental composition and distribution within the objects, as well as the identification of the nature and distribution of the corrosion products. Ideally the identification method should cause no alteration in the sample. In this work, different archaeological pieces with a gilded look have been characterized using simultaneously PIXE and RBS at the CMAM external microprobe in order to study the gilding metalworking done in the Iberian Peninsula during the Middle Ages. The gold layer thickness and its elemental concentrations of Ag, Au and Hg were determined by both techniques and compared with the scanning electron microscopy images obtained for some fragments of pieces. PACS  29.30.Kv; 87.64.-t