Electrochemistry of coordination compounds : XVI. New mixed 1,2-bis(diphenylphosphino)ethaneacetonitrile or -carbon monoxide iron(II), iron(I) and iron(0) complexes

The new iron compound, trans-[Fe(DPE)₂(MeCN)₂] (ClO₄)₂ (DPE=PPh₂CH₂CH₂PPh₂), has been prepared and investigated electrochemically. In acetonitrile the complex shows two reduction steps, consistent with the formation of the stable iron(I) species, [Fe(DPE)₂(MeCN)]⁺ and the rather labile π-bonded acetonitrile adduct, Fe(DPE)₂(π-MeCN), respectively. Acetonitrile substitution by carbon monoxide leads to formation of the carbonylated species, which have been characterized, and examined by electrochemical techniques. A significant feature is that trans-[Fe(CO)₂(DPE)₂]²⁺, unlike trans-[Fe(DPE)₂(MeCN)₂]²⁺, takes up two electrons in a single process, the unstable d⁷ intermediate undergoing a fast disproportionation. A tentative interpretation of this behaviour is suggested.     

Reactivity of 2-amino-1,3,4-thiadiazoles. Nucleophilic behaviour of some 2-amino-1,3,4-thiadiazoles: Model compounds

The ambident nucleophilic behaviour of some 2-amino-5-H-1,3,4-thiadiazoles in alkylation, acylation and nitrosation reaction has been verified. The structures assigned to the 2-amino-1,3,4-thiadiazoles ( 1a-i ) and to the Δ²-1,3,4-thiadiazolines ( 2a-e ) agree with the spectral data.     

Detection of a stable nitroxide during chemical depolymerization of heparin

The use of low-molecular-weight heparins (LMWHs) has become common, since compared to unfractionated heparin (UFH), they have a much longer plasma half-life and lower incidence of side effects. LMWHs are derived from the depolymerization of UFH, obtained either chemically, physically or enzymatically. We employed electron spin resonance (ESR) spectroscopy to study the depolymerization of UFH by copper in the presence of hydrogen peroxide. A stable nitroxide radical was detected. This could be generated by the hydroxyl radical attack either to the N-SO⁻₃ group or to free amino groups present in the UFH preparation.     

Photochemically modulated endothelial cell thrombogenicity via the thrombomodulin-tissue factor pathways

Photodynamic therapy (PDT) is based on a photochemical reaction using a photosensitizer and light to produce reactive oxygen species that have biological effects. Although its application in some fields is largely based on thrombosis, in the vascular setting thrombosis must be prevented. In this study we examined the effects of PDT on the changes in activity of thrombomodulin (TM) and tissue factor (TF) as important regulators of the coagulation process of endothelial cells. Human umbilical vein endothelial cells were treated with PDT (chloro-aluminum-sulfonated phthalocyanine, lambda = 630 nm) at different light-energy doses, and TM and TF levels were measured using fluorescence spectroscopy. Microparticles (MP) were analyzed using flow cytometry analysis. PDT alters the thrombogenic state of endothelial cells by causing decreased expression of TM and increased expression of functional TF in a light-energy dose-dependent way. PDT-treated endothelial cells shed large numbers of MP containing high levels of TF. TF functionality of PDT-treated cells, measured by a Factor Xa-generating assay, was high. TF was located mostly intracellularly and in MP. The disturbed anticoagulant balance described in this study may explain the occurrence of thrombosis induced by PDT and, if not contained, dispute the suitability of PDT as an adjuvant modality to treat vascular restenosis.     

Environmental effects on a prion's helix II domain: copper(II) and membrane interactions with PrP180-193 and its analogues

An abnormal interaction between copper and the prion protein is believed to play a pivotal role in the pathogenesis of prion diseases. Copper binding has been mainly attributed to the N-terminal domain of the prion protein, but this hypothesis has recently been challenged in some papers which suggest that the C-terminal domain might also compete for metal anchoring. In particular, the segment corresponding to the helix II region of the prion protein, namely PrP180-193, has been shown both to bind copper and to exhibit a copper-enhanced cytotoxicity, as well as to interact with artificial membranes. The present work is aimed at extending these results by choosing the most representative model of this domain and by determining its copper affinity. With this aim, the different role played by the electrostatic properties of the C- and N-termini of PrP180-193 (VNITIKQHTVTTTT) in determining its conformational behaviour, copper coordination and ability to perturb model membranes was investigated. Owing to the low solubility of PrP180-193, its copper affinity was evaluated by using the shorter PrPAc184-188NH2 (IKQHT) analogue as a model. ESI-MS, ESR, UV/Vis, and CD measurements were carried out on the copper(II)/PrPAc184-188NH2 and copper(II)/PrP180-193NH2 systems, and showed that PrPAc184-188NH2 is a reliable model for the metal interaction with the helix II domain. The affinity of copper(II) for the helix II fragment is higher than that for the octarepeat and PrP106-126 peptides. Finally, the different ability of PrP180-193 analogues to perturb the DPPC model membrane was assessed by DSC measurements. The possible biological consequences of these findings are also discussed briefly.     

The relative permittivity of 1,2-ethanediol+2-methoxyethanol+water ternary mixtures

The relative permittivities for the ternary 1,2-ethanediol (component 1) + 2-methoxyethanol (2) + water (3) solvent system have been measured for 66 mixtures covering the whole mole fraction composition 0X₁/X₂/X₃ 1 range at –10, –5 and 0 °C. The experimental data were used to test some empirical relations stating the dependence of = (X₁, X₂, X₃). A comparison between the calculated and experimental data show that these equations can be usefully employed to predict values in correspondence of the experimental data gaps.     

Nonlinear equations related to the Levi form

Si considera l’equazione di Levi su un aperto di e si studiano alcune proprietà delle sue soluzioni regolari.     

The set union problem with dynamic weighted backtracking

We consider an extension of the set union problem, in which dynamic weighted backtracking over sequences of unions is permitted. We present a new data structure which can support each operation inO(logn) time in the worst case. We prove that this bound is tight for pointer based algorithms. Furthermore, we design a different data structure to achieve better amortized bounds. The space complexity of both our data structures isO(n). Motivations for studying this problem arise in logic programming memory management.Work partially supported by NSF Grant CCR-88-14977, by the ESPRIT II Basic Research Actions Program of the EC under contract No. 3075 (Project ALCOM), and by the Italian MURST Project Algoritmi e Strutture di Calcolo.Partially supported by an IBM Graduate Fellowship.     

Axiomatic foundations of quantum physics: Critiques and misunderstandings. Piron's question-proposition system

Some of the most frequent misconceptions about axiomatic quantum physics are discussed with the aim of clarifying their true significance, taking Piron's approach as conceptual framework. In particular, we deal with the following topics: the wrong identification of Piron's questions and Mackey's questions, and some curious alleged empirical consequences; the role of propositions as suitable equivalence classes of questions, their partial order structure, and the paradoxical consequences of the erroneous assignment to questions of some lattice properties involving propositions; the logical and the empirical purport of some negative theorems; the standard Hilbert space model of the theory and the consequent metaphysical disasters related to some identifications, which are peculiar of this model. A controversy between Foulis-Piron-Randall and Hadjisavvas-Thieffine-Mugur-Schächter is analyzed on the basis of the proposed Hilbert space model (in which Piron's questions are realized by Hilbertian effects, i.e., linear bounded operatorsF such that which clarify the different point of views. As an example, we treat the unsharp localization operators inL ₂().     

Optimizing separation conditions for riboflavin,flavin mononucleotide and flavin adenine dinucleotide in capillary zone electrophoresis with laser-induced fluorescence detection

DNA sequencing is performed in a multiplexed capillary electrophoresis system by UV absorption detection. Four individual electropherograms are obtained by simultaneously running the unlabeled DNA products of the four ddNTP-terminated reactions in the capillary array. The sequence of the template used in the cycle-sequencing reaction can be determined by overlaying the four electropherograms. Two internal standards are employed to adjust for the variance in migration times among the capillaries. After applying the correction algorithm, base calling can be done at a high level of confidence.