Copper corrosion in buffered and non-buffered synthetic seawater: a comparative study

The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s^–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater.     

Ethylenic compounds reactivity: bromination—XLI: Relative reactivities of R1CMeCH2 and R1CHCMe2 series as a criterion for distinguishing between bridged and acyclic transition states. Degree of symmetry of the bromonium ion-like transition state

Reactivities of homogeneous series of ethylenic compounds R¹CHCH₂1, trans R¹CHCHMe 2, R¹MeCCH₂3 and R¹CHCMe₂4 have been measured in methanol at 25°C (R¹ Me, Et, n-Pr, -CH₂C₆H₅-CH₂OCOCH₃, -CH₂Cl). The criterion developed to decide between a bridged and a carbonium ion-like transition state is based on an internal comparison of the series and avoids resorting to external structural scales. Even in the case of alkenes 3 and 4 which are very dissymmetric with respect to polarity, the sensitivity to polar effects remains constant and the transition state behaves like a symmetric entity; only a slight secondary effect, attributed to hyperconjugation, is detectable.     

Regioselectivity of Birch reductive alkylation of biaryls

[reaction: see text] The regioselectivity of the Birch reductive alkylation of polysubstituted biaryls has been investigated. Results indicate that regioselectivity is affected by the electronic nature of substituents on both aromatic rings. The electron-rich 3,5-dimethoxyphenyl moiety is selectively reduced and then alkylated, while phenols and aniline are not dearomatized under these conditions. Biaryls possessing a phenol moiety are alkylated on the second ring, providing that the acidic proton has been removed prior to the Li/NH3 reduction.     

Synthesis of 2′,3′-dihydrosolanesyl analogues of β-d-arabinofuranosyl-1-monophosphoryldecaprenol with promising antimycobacterial activity

Two new hydrolytically stable analogues of β-d-arabinofuranosyl-1-monophosphoryldecaprenol, the donor substrate for mycobacterial arabinosyltransferase, have been prepared. Biological evaluation of these compounds in vitro against Mycobacterium tuberculosis H₃₇Rv strain revealed a promising activity.     

Calix[6]arene-based cuprous "funnel complexes": a mimic for the substrate access channel to metalloenzyme active sites

Two calixarene-based model systems (a and b) for monocopper enzymes are compared. Both present a tris(pyridine) coordination site for Cu that mimics the imidazole-rich neutral binding site in enzymes. Upon reaction with 1 equiv of copper(I), the tridentate ligands gave rise to ill-defined unsymmetrical complexes. However, in the presence of an organonitrile RCN (R = Me, Et, Ph), tetrahedral species were obtained, with the nitrilo ligand included in the calixarene hydrophobic cone. System b presents a larger cavity than system a, with a wider opening thanks to the removal of three tBu groups from the calixarene structure. As a result, the recognition pattern for MeCN vs PhCN is inverted, and the relative affinity constants differ by 3 orders of magnitude. The mechanism of the acetonitrile exchange at the cuprous centers was studied by (1)H NMR spectroscopy. Thermodynamic and kinetic data show that it follows a dissociative pathway in both cases. The main differences between systems a and b stem from the presence of a door that entraps the guest in case a. In system b indeed, the removal of three calixarene tBu groups led to a 100-fold acceleration of the MeCN exchange rate. Hence, these supramolecular systems provide a rare and interesting model for the hydrophobic substrate channel giving access to a metalloenzyme active site.     

Efficient primer strand extension beyond oxadiazole carboxamide nucleobases

Two oxadiazole carboxamide deoxyribonucleoside analogues are described that can be incorporated and efficiently extended by Taq DNA polymerase. The primer strand extension beyond oxadiazole nucleoside analogues occurs at rates similar to the values observed for the canonical Watson-Crick base pairs irrespective of the template nucleobase. These distinctive chemical effects in DNA polymerase extensions are attributed to the smaller size and unique electronic properties of the oxadiazole nucleobase.     

Direct N- and C-alkenylation of nitrogen-containing heterocycles with magnesium alkylidene carbenoids

Treatment of magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at −78 °C in toluene, with N-lithio nitrogen-containing heterocycles gave N-alkenylated products in moderate to good yields. Also, the reaction of C-lithio indoles, which were generated from N-protected indoles, with magnesium alkylidene carbenoids gave C-2 or C-3 alkenylated products, corresponding to the protective group. The intermediate of these reactions were found to be the alkenyl anion, which could be trapped with electrophiles to give the heterocycles having fully substituted alkenes.     

Examining the balance between efficiency and resilience in closed-loop supply chains

Central European Journal of Operations Research - We study a hybrid system where the demand of customers can be satisfied by both manufacturing new products and remanufacturing used products. To...     

Triangulations and moduli spaces of Riemann surfaces with group actions

Summary We study that subset of the moduli space of stable genusg,g>1, Riemann surfaces which consists of such stable Riemann surfaces on which a given finite groupF acts. We show first that this subset is compact. It turns out that, for general finite groupsF, the above subset is not connected. We show, however, that for ℤ₂ actions this subsetis connected. Finally, we show that even in the moduli space ofsmooth genusg Riemann surfaces, the subset of those Riemann surfaces on which ℤ₂ actsis connected. In view of deliberations of Klein ([8]), this was somewhat surprising. These results are based on new coordinates for moduli spaces. These coordinates are obtained by certainregular triangulations of Riemann surfaces. These triangulations play an important role also elsewhere, for instance in approximating eigenfunctions of the Laplace operator numerically. This work has been supported by the European Communities Science Plan Project No SCI^*-CT91 (TSTS) “Computational Methods in the Theory of Riemann Surfaces and Algebraic Curves,” by Academy of Finland and by the Swiss National Science Foundation Grant 20-34099.92. We thank M. C. Petrus for providing excellent motivation for this work. This article was processed by the author using the LATEX style filecljourl from Springer-Verlag.