Electrochemistry of cytochrome c incorporated in Langmuir-Blodgett films of Nafion and Eastman AQ 55

Ultrathin films of Nafion and Eastman-AQ 55 loaded with cytochrome c (cyt c) were obtained and transferred on indium tin oxide (ITO) electrodes via the Langmuir-Blodgett (LB) technique. The pressure-area isotherms for mixed ionomer-protein films indicate that the miscibility of cyt c in the interfacial layer is better for Nafion than for AQ 55. Interestingly, these composite films maintain the electroactivity of cyt c without requiring the addition of promoters or mediators. Both for AQ 55-cyt c and Nafion-cyt c films, the half-wave potential for the reversible reduction of ferricytochrome c corresponds to the value expected for the weakly adsorbed protein. The modified electrodes show electrocatalytic reaction with ascorbate anion. Comparison with previous literature reports indicate that for Nafion the LB coating procedure is unique in keeping the electroactivity of cyt c.     

A new and effective route to (±)-botryodiplodin and (±)-epi-botryodiplodin acetates using a halogen atom transfer Ueno-Stork cyclization

(±)-Botryodiplodin and (±)-epi-botryodiplodin acetates were prepared in good yields following a practical four step route. The method, for the construction of the strategic tetrahydrofuran ring, hinged on an unprecedented halogen atom transfer Ueno-Stork cyclization of an O-allyl α,α-dihalohemiacetal acetate, catalyzed by the redox complex CuCl/N,N,N′,N″,N″-pentamethyldiethylenetriamine.     

Chemical analyses of heavy metal contamination in sediments of the Venice Lagoon and toxicological implications

Heavy metals are extracted from sediments using 1 M HCl; then, solutions are neutralised with 1 M NaOH, to fit the conditions suitable for the Vibrio Fischeri test. In the neutralised solutions different percentages of initial metal concentration are present, depending on the individual solubilities. The chemical investigation of the metal fraction extracted from the sediment with this procedure and the different metal bioavailability depending on the presence of natural complexing agents are the subject of this work. The results obtained confirm the good agreement between heavy metal fraction extracted using 1 M HCl and the anthropogenic component in the sediment. The use of voltammetric techniques, and the addition of low molecular weight humic acids into extracts show the ability of natural complexing agents in affecting heavy metal bioavailability and toxicity.     

Determination of heavy metals in real samples by anodic stripping voltammetry with mercury microelectrodes : Part 2. Application to Rain and Sea Waters

Differential-pulse anodic stripping voltammetry at a mercury microelectrode is applied to determine labile and total zinc, cadmium, lead and copper in samples of rain and sea water. The low ohmic drop associated with microelectrodes permits reliable measurements in rain water without addition of supporting electrolyte. The values found in a typical sample were 0.95 μg l^?1 Cu, 0.38 μg l^?1 Pb, 0.01 μg l^?1 Cd and 0.95 μg l^?1 Zn, with relative standard deviations in the range 4–18%. The small effects of organic matter at microelectrodes, compared with those at a hanging mercury drop electrode, allow sensitive and reliable measurements of labile metals in surface sea water. Total metal concentrations are determined after acidification to pH 1.5 with hydrochloric acid. The results are compared with those obtained with atomic absorption spectrometry and with differential-pulse anodic stripping voltammetry at conventional mercury electrodes. Satisfactory results were obtained for a reference sea water.     

A short approach to chaetomellic anhydride A from 2,2-dichloropalmitic acid: elucidation of the mechanism governing the functional rearrangement of the chlorinated pyrrolidin-2-one intermediate

Chaetomellic anhydride A was efficiently attained in three steps, starting from 2,2-dichloropalmitic acid and 2-(3-chloro-2-propenylamino)pyridine. Atom transfer radical cyclisation selectively formed the cis-stereoisomer of the trichloropyrrolidin-2-one, which underwent a stereospecific functional rearrangement to form a substituted maleimide. The choice of 2-pyridyl, as ‘cyclisation auxiliary’ in the atom transfer radical cyclisation step, proved beneficial for hydrolysis of the maleimide to form the desired anhydride.     

EPR and ab-initio study on the solid state radiolysis of aliphatic and aromatic polyesters

Low temperature matrix EPR spectroscopy was employed to investigate the free radical intermediates in the solid state radiolysis of poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(ethylene naphthalate) (PEN), poly(1,4-cyclohexanedimethylene terephthalate-co-ethylene terephthalate) (PCT-co-ET) and poly(ethylene adipate) (PEA). With PEA the species identified is consistent with the formation of carbon centred radicals stemming from electron capture, C–O scissions and H abstractions, the most abundant species at room temperature being the -ester radical, –CH₂–CH–COO–. The radiolysis of PEN is characterized by the predominance of radicals arising from the aromatic section, the preferred reaction being the H atom addition at a position adjacent to the ester unit, leading to the formation of cyclohexadienyl type radicals. In the copolymer, PET and PBT, the role played by the aliphatic and aromatic sections with respect to radical forming processes is of comparable importance. The cyclohexadienyl radicals arising from these latter polymers are reckoned with the prominent H addition at the sites adjacent to the esters groups which are also statistically favoured. The reactivity distribution in the aromatic rings with respect to the formation of cyclohexadienyls was analyzed in greater detail by comparing the experimental results with DFT B3LYP M.O. calculations. The DFT method has also been employed for assessing the EPR properties of the cyclohexadienyl and ion-radicals from PEN and PET models.     

The influence of different loads on the remodeling process of a bone and bioresorbable material mixture with voids

A model of a mixture of bone tissue and bioresorbable material with voids was used to numerically analyze the physiological balance between the processes of bone growth and resorption and artificial material resorption in a plate-like sample. The adopted model was derived from a theory for the behavior of porous solids in which the matrix material is linearly elastic and the interstices are void of material. The specimen—constituted by a region of bone living tissue and one of bioresorbable material—was acted by different in-plane loading conditions, namely pure bending and shear. Ranges of load magnitudes were identified within which physiological states become possible. Furthermore, the consequences of applying different loading conditions are examined at the end of the remodeling process. In particular, maximum value of bone and material mass densities, and extensions of the zones where bone is reconstructed were identified and compared in the two different load conditions. From the practical view point, during surgery planning and later rehabilitation, some choice of the following parameters is given: porosity of the graft, material characteristics of the graft, and adjustment of initial mixture tissue/bioresorbable material and later, during healing and remodeling, optimal loading conditions.     

Soft-impact dynamics of deformable bodies

Systems constituted by impacting beams and rods of non-negligible mass are often encountered in many applications of engineering practice. The impact between two rigid bodies is an intrinsically indeterminate problem due to the arbitrariness of the velocities after the instantaneous impact and implicates an infinite value of the contact force. The arbitrariness of after-impact velocities is solved by releasing the impenetrability condition as an internal constraint of the bodies and by allowing for elastic deformations at contact during an impact of finite duration. In this paper, the latter goal is achieved by interposing a concentrate spring between a beam and a rod at their contact point, simulating the deformability of impacting bodies at the interaction zones. A reliable and convenient method for determining impact forces is also presented. An example of engineering interest is carried out: a flexible beam that impacts on an axially deformable strut. The solution of motion under a harmonic excitation of the beam built-in base is found in terms of transverse and axial displacements of the beam and rod, respectively, by superimposition of a finite number of modal contributions. Numerical investigations are performed in order to examine the influence of the rigidity of the contact spring and of the ratio between the first natural frequencies of the beam and the rod, respectively, on the system response, namely impact velocity, maximum displacement, spring stretching and contact force. Impact velocity diagrams, nonlinear resonance curves and phase portraits are presented to determine regions of periodic motion with impacts and the appearance of chaotic solutions, and parameter ranges where the functionality of the non-structural element is at risk.