Direct electrochemical reduction of spinach and desulfovibrio desulfuricans Norway ferredoxins

Electrochemical techniques were used to study the reduction-reoxidation of spinach and Desulfovibrio desulfuricans ferredoxins in the presence of poly- -lysine. A peak corresponding to the reduction of native molecules was detected by differential pulse polarography and voltammetry at the basal-plane pyrolytic graphite electrode. The existence of reduction-reoxidation process was evidenced by cyclic voltammetry. The redox potential values of −0.42±0.01 V (spinach ferredoxin), −0.37±0.01 V (D. desulfuricans ferredoxin I), −0.41±0.01 V (D. desulfuricans ferredoxin II) were obtained. No changes in redox potential values were detected in the pH range 5–9.5. The presence of poly- -lysine promotes the electron transfer between the electrode and the ferredoxin molecules. It is suggested that several factors such as electrostatic interactions and the close environment of clusters can influence the electron transfer rates of heterogeneous exchange between the electrode and the ferredoxin molecules.     

Variations of iridoid oleuropein in Italian olive varieties during growth and maturation

This research paper reports on the concentrations of oleuropein in fruits of seven Italian olive cultivars. These oleuropein levels, during fruit growth and maturation, were monitored by taking olive samples from the same olive trees grown in Middle Italy. A novel high‐resolution gas chromatography (HRGC) oleuropein quantification method and a new high‐performance liquid chromatography (HPLC) method were developed. The olive fruits showed high contents of oleuropein, which were greatly influenced by the olive cultivar (genetic store) factor. The stage of fruit growth and maturation was another factor strongly affecting the contents of iridoid oleuropein in olive drupes, whatever the olive cultivar considered. Green olives had much higher concentrations of this biofunctional glucoside, which decreased regularly during fruit growth and ripeness. No differences were observed between the two developed oleuropein quantification methods, which gave, for all the olive cultivars, average values of fruit oleuropein contents that were not statistically different. These two reliable repetitive methods, noticeably the HPLC one (which also showed a lower running time), could be used for routine determination of oleuropein in olive drupes. We observed that, in general, olive cultivars having high oleuropein concentrations in the fruits were also characterized by marked oleuropein contents in the leaves.     

HS-SPME coupled to GC/MS for quality control of Juniperus communis L. berries used for gin aromatization

HS-SPME coupled to GC/MS was applied to the analysis of the volatile fraction of Juniperus communis L. berries, which are the principal ingredient used for gin aromatization. Seventy seven compounds were identified by comparison with reference compounds or tentatively identified by comparing their mass spectra and retention index with those reported in mass spectra libraries and literature, respectively. Seventy four were detected by SPME and sixty eight were detected by solvent distillation extraction (SDE). These were mainly mono- and sesquiterpenic compounds that represented more than the 80% of the gin’s volatile composition. A high percent content was due to monoterpenoids, whose analysis could be important for the assessment of sensory quality control of juniper due to their impact on gin aroma. The main monoterpenoids detected in the headspace of the juniper berries from two periods of collection were terpinen-4-ol, p-cymene, β-myrcene, γ-terpinene, α-pinene and limonene. These represented more than the 70% of the sample’s volatile fraction. The proposed SPME method required short times and the low cost of analysis and enabled to detect a number of compounds comparable with SDE or much higher than the number of compounds reported by other extraction techniques. The results suggested the suitability of this technique for the assessment of the volatile composition of juniper berries intended for gin flavouring.     

Lithiated short side chain perfluorinated sulfonic ionomeric membranes: Water content and conductivity

In view of possible applications as single-ion electrolyte for lithium batteries, some aspects of the lithium form of Hyflon Ion ionomer, a sulfonic short side chain (SSC) electrolyte, have been investigated. The synthesis of the ionomer and the successive membrane preparation is reported. An appropriate methodology for the direct salification of the ionomeric membrane from the SO₂F form to lithium salt, using lithium hydroxide in absence of organic solvent has been found. Utilizing these SSC lithium ionomer membranes and though a particular methodology for the dehydration of the lithium ion membrane in non-aqueous media, it has been possible to achieve an ionic conductivity of 10⁻³ S cm⁻¹ at room temperature [W. Navarrini, S. Panero, B. Scrosati, A. Sanguineti, European Patent 1,403,958 A1 (2003)]. Surprisingly it was observed that the membrane ionic conductivity depends on the dehydration methodologies adopted.     

Proton-conducting membranes based on protic ionic liquids

New classes of proton-conducting membranes formed by incorporating Brönsted acid–base ionic liquids in a poly(vinyldenefluoride-co-hexafluoropropylene) PVdF polymer matrix, are here reported and discussed. We show that these membranes are characterized by high, thermally stable proton conductivity. However, this favourable property is in part contrasted by the release of the ionic liquid component, which may affect the long-term stability of the membranes. Various strategies are underway in our laboratory to solve this issue, and in this work we describe one of them, based on the dispersion of selected ceramic fillers in the polymer matrix. We show that this approach, while successful in enhancing the conductivity of the membranes, is not much effective in preventing the release of the ionic liquid component and thus, that other roads have to be explored to reach a satisfactory improvement of the integrity of the membrane.     

Greywater recycling in Vietnam — Application of the HUBER MBR process

Greywater is the part of domestic wastewater that is free of faeces. The volume and concentration of this separately collected wastewater flow depend on the consumer behaviour and vary according to its source. The average amount of greywater produced per day in a German household is 70 l per person, which is more than 50% of the total wastewater production [5]. This figure corresponds with the average figures provided for Chinese households (80 l per person/day, GB/T 50331-2002), but significantly exceeds the South African average of 20 l per person and day [1].Compared to domestic wastewater, greywater generally contains less organic pollutants, less nutrients but a high amount of tensides. The effluent from bath tubs, showers or wash hand basins contains for example a by approx. two decimal orders lower number of total and faecal coliform bacteria (Escherichiacoli) [2] and [6].Due to its relatively low content of pollutants, greywater is easy to treat with MBRs. The pollutants contained are decomposed by the bacteria of the activated sludge tank. The following membrane filtration unit separates the treated greywater from the activated sludge. The treated greywater is of high quality and hygienically safe so that it can be reused, alone or combined with rain water, for toilet flushing water, laundry washing or for irrigation purposes.Within the scope of the SANSED II research project HUBER has been successful in adapting the MBR system for greywater treatment to the specific conditions in Vietnam and testing the system in operation in a small city in the Mekong delta, South Vietnam. The wastewater from kitchen sinks and the bathrooms of a dormitory on the campus of Can Tho University was clarified in the HUBER GreyUse^® plant over a period of three months. The project aim was the production of high quality service water from greywater for safe reuse as toilet flush water.     

Modulation on C‐ and N‐Terminal Moieties of a Series of Potent and Selective Linear Tachykinin NK2 Receptor Antagonists

Herein we describe the synthesis of a series of new potent tachykinin NK₂ receptor antagonists by the modulation of the C‐ and N‐terminal moieties of ibodutant (MEN 15596, 1 ). The N‐terminal benzo[b]thiophene ring was replaced by different substituted naphthalenes and benzofurans, while further modifications were evaluated at the C‐terminal tetrahydropyran moiety. Most compounds demonstrated a high affinity for the human NK₂ receptor and high in vitro antagonist potency, indicating that a wide range of substituents at both termini can be incorporated in the molecule without detrimental effects on the interactions with the NK₂ receptor. Selected compounds were tested in vivo confirming their activity as NK₂ antagonists. In particular, after both iv and id administration to guinea pig, compound 61 b was able to antagonize NK₂‐induced colonic contractions with a potency and duration‐of‐action fully comparable to the reference compound 1 (MEN 15596, ibodutant).     

Towards biomimetic models of the reduced [FeFe]-hydrogenase that preserve the key structural features of the enzyme active site; a DFT investigation

[FeFe]-hydrogenases are the most efficient biological catalysts available for the H₂ evolution reaction. Their active site – the H-cluster – features a diiron subsite which has the peculiar characteristic of bearing cyanide groups hydrogen-bonded to the apoprotein as well as carbonyl ligands. Notably, one of the CO ligands is disposed in bridging position between the metal centers. This allows one of the Fe ions to retain a square pyramidal coordination – which determines the assumption of the so-called “rotated structure” – with a vacant coordination site in trans to the μ-CO group, ready to bind protons when the active site is in the Fe^IFe^I state. Many Fe^IFe^I biomimetic models have been synthesized and characterized so far, but most of them fail to reproduce the orientation of the diatomic ligands that is observed in the enzyme active site.     

Evaluation of friction condition in cold forging by using T-shape compression test

Friction plays an important role in metal forming, and numerical simulation of forging processes requires precise informations about the material properties and the value of the friction factor m or coefficient μ. This paper describes the T-shape compression, a new friction testing method by combined compression and extrusion of a cylinder between a flat punch and a V-grooved die. It can realize actual cold forging condition and allows measuring the friction on the cylindrical surface of the billet during forging process. The results of experiments and simulations show that the stroke–load curve and the height of the extruded part are both sensitive to friction. In order to obtain the highest sensitivity to friction, a FE parametric study of this test has been performed: it indicates that small corner radius and V-groove angle in the die should be chosen. Two commercial FE codes, FORGE 3D and ABAQUS, were used and provided very similar results for a given friction condition. Low carbon steel drawn bar with phosphate and soap coating was chosen as specimens. Friction tests with three different lubrication conditions (solid coating, oil and oil + solid coating) were carried out, and then friction factor m and friction coefficient μ were determined by using experimental results and the calibration by numerical simulation of T-shape compression test.