Cover Picture

The cover picture shows how thrombosis occurs in the deep veins of the lower limbs. Stasis, which results from slow and turbulent blood flow, combined with hypercoagulation, caused, for example, by a surgical procedure, may result in thrombus formation. The synthetic sulfated pentasaccharide shown in part is a potent antithrombotic compound that exerts its effect by activation of the plasma protein antithrombin III. Conformationally locked monosaccharides have now been synthesized to demonstrate that L-iduronic acid, one part of the pentasaccharide, must adopt an unusual distorted conformation to activate antithrombin III. Such conformational effects might be relevant in explaining the unique biological properties of glycosaminoglycans that contain L-iduronic acid. In the background of the picture, a flight of vampire bats is attracted by the pentasaccharide. Vampire was the name given to South American blood-sucking bats (Latin name: desmodus rotundus) in 1761 by the French naturalist Georges Louis Leclerc Comte de Buffon (1707-1788). These bats are known to attack cattle and, very rarely, sleeping human beings. Although their saliva has been shown to contain an anticoagulant compound, they would also be happy to benefit from the pentasaccharide mentioned above, to suck the blood out of the vein more easily. More details about this compound which would be helpful to vampire bats are reported by Petitou, Sina? et al. on p. 1670 ff.     

Frequency-coded quantum key distribution

We report an intrinsically stable quantum key distribution scheme based on genuine frequency-coded quantum states. The qubits are efficiently processed without fiber interferometers by fully exploiting the nonlinear interaction occurring in electro-optic phase modulators. The system requires only integrated off-the-shelf devices and could be used with a true single-photon source. Preliminary experiments have been performed with weak laser pulses and have demonstrated the feasibility of this new setup.     

Conductivity of irradiated Kapton in relation to energy loss of ions and electrons

Abstract

We have studied the effects of 2.5 MeV electron irradiation and ion (C, N, F, Si and Kr) bombardment on the electrical conductivity of a polyimide (Kapton-H) with ion energies ranging between 320 keV (N) and 1.25 GeV (Kr). In this wide range of situations we have tried to sort out the respective effects of nuclear and electronic excitation energy losses.

For all ion irradiation the conductivity is found to scale with the electronic excitation absorbed dose: i.e. a power law of conductivity versus absorbed dose with an exponent around 9 is observed. At a given absorbed dose (in Gray units) the efficiency of each ion to enhance conductivity is found to be proportional to the electronic energy loss; electrons are much less efficient than ions and thus collective excitations are required to achieve this process.

The nuclear energy loss can perhaps play some role at conductivities higher than 100 Ω^?1 m^?1, but its effects are negligible in the range explored here.     

The pyridyl-tag strategy applied to the hydrocarbon/perfluorocarbon phase-switching of a porphyrin and a fullerene

A new hydrocarbon/perfluorocarbon phase-switching strategy based on coordination of pyridyl-tagged molecules to a highly fluorinated dicopper-carboxylate complex possessing two accessible axial coordination sites is described. When a chloroform solution of the tetrapyridyl-substituted porphyrin 3 (0.1 mM, 2 mL) is layered on a perfluorodecalin solution of 2 (3.25 mM, 1.5 mL), complete extraction of the porphyrin into the fluorous phase is observed after 30 min of stirring. Quantitative release of both the porphyrin and 2 is achieved simply by adding excess THF to the biphasic system, the THF acting as a pyridine competing ligand. The recovered perfluorocarbon solution containing 2 can be reused for another complexation with the same efficiency. The scope of this approach is emphasized by the phase-switching of a dipyridyl-substituted fullerene, another example of a molecule for which solubilization in perfluorocarbons is very challenging.     

Biosensors based on enzyme field-effect transistors for determination of some substrates and inhibitors

This paper is a review of the authors' publications concerning the development of biosensors based on enzyme field-effect transistors (ENFETs) for direct substrates or inhibitors analysis. Such biosensors were designed by using immobilised enzymes and ion-selective field-effect transistors (ISFETs). Highly specific, sensitive, simple, fast and cheap determination of different substances renders them as promising tools in medicine, biotechnology, environmental control, agriculture and the food industry.The biosensors based on ENFETs and direct enzyme analysis for determination of concentrations of different substrates (glucose, urea, penicillin, formaldehyde, creatinine, etc.) have been developed and their laboratory prototypes were fabricated. Improvement of the analytical characteristics of such biosensors may be achieved by using a differential mode of measurement, working solutions with different buffer concentrations and specific agents, negatively or positively charged additional membranes, or genetically modified enzymes. These approaches allow one to decrease the effect of the buffer capacity influence on the sensor response in an aim to increase the sensitivity of the biosensors and to extend their dynamic ranges.Biosensors for the determination of concentrations of different toxic substances (organophosphorous pesticides, heavy metal ions, hypochlorite, glycoalkaloids, etc.) were designed on the basis of reversible and/or irreversible enzyme inhibition effect(s). The conception of an enzymatic multibiosensor for the determination of different toxic substances based on the enzyme inhibition effect is also described.We will discuss the respective advantages and disadvantages of biosensors based on the ENFETs developed and also demonstrate their practical application.     

A dinuclear manganese(II) complex with the [Mn(2)(mu-O(2)CCH(3))(3)](+) core: synthesis, structure, characterization, electroinduced transformation, and catalase-like activity

Reactions of Mn(II)(PF(6))(2) and Mn(II)(O(2)CCH(3))(2).4H(2)O with the tridentate facially capping ligand N,N-bis(2-pyridylmethyl)ethylamine (bpea) in ethanol solutions afforded the mononuclear [Mn(II)(bpea)](PF(6))(2) (1) and the new binuclear [Mn(2)(II,II)(mu-O(2)CCH(3))(3)(bpea)(2)](PF(6)) (2) manganese(II) compounds, respectively. Both 1 and 2 were characterized by X-ray crystallographic studies. Complex 1 crystallizes in the monoclinic system, space group P2(1)/n, with a = 11.9288(7) A, b = 22.5424(13) A, c =13.0773(7) A, alpha = 90 degrees, beta = 100.5780(10 degrees ), gamma = 90 degrees, and Z = 4. Crystals of complex 2 are orthorhombic, space group C222(1), with a = 12.5686(16) A, b = 14.4059(16) A, c = 22.515(3) A, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, and Z = 4. The three acetates bridge the two Mn(II) centers in a mu(1,3) syn-syn mode, with a Mn-Mn separation of 3.915 A. A detailed study of the electrochemical behavior of 1 and 2 in CH(3)CN medium has been made. Successive controlled potential oxidations at 0.6 and 0.9 V vs Ag/Ag(+) for a 10 mM solution of 2 allowed the selective and nearly quantitative formation of [Mn(III)(2)(mu-O)(mu-O(2)CCH(3))(2)(bpea)(2)](2+) (3) and [Mn(IV)(2)(mu-O)(2)(mu-O(2)CCH(3))(bpea)(2)](3+) (4), respectively. These results have shown that each substitution of an acetate group by an oxo group is induced by a two-electron oxidation of the corresponding dimanganese complexes. Similar transformations have been obtained if 2 is formed in situ either by direct mixing of Mn(2+) cations, bpea ligand, and CH(3)COO(-) anions with a 1:1:3 stoichiometry or by mixing of 1 and CH(3)COO(-) with a 1:1.5 stoichiometry. Associated electrochemical back-transformations were investigated. 2, 3, and the dimanganese [Mn(III)Mn(IV)(mu-O)(2)(mu-O(2)CCH(3))(bpea)(2)](2+) analogue (5) were also studied for their ability to disproportionate hydrogen peroxide. 2 is far more active compared to 3 and 5. The EPR monitoring of the catalase-like activity has shown that the same species are present in the reaction mixture albeit in slightly different proportions. 2 operates probably along a mechanism different from that of 3 and 5, and the formation of 3 competes with the disproportionation reaction catalyzed by 2. Indeed a solution of 2 exhibits the same activity as 3 for the disproportionation reaction of a second batch of H(2)O(2) indicating that 3 is formed in the course of the reaction.     

On the clarification of the IR stretching vibration assignment of adsorbed N2 on Rh0 and Rhdelta+ surface atoms of supported Rh crystallites

The low-temperature adsorption of N(2) on Rh/SiO(2) samples of various particle-size distributions was followed by FTIR. The addition of O(2) pulses on Rh(0) surfaces saturated with chemisorbed N(2) allowed us to reassign stretching frequencies attributed originally to N(2)-Rh(0) to N(2)-Rh(delta+). The formation of the latter oxidized Rh species is assumed to be induced by an electron withdrawal from adsorbed oxygen species on Rh surface centers neighboring those onto which N(2) species are chemisorbed. The present work, thus, enables us to delimit ranges of frequencies for which the adsorption of N(2) can be considered to occur on either Rh(0) or Rh(delta+) centers for nu(N2) lower or higher than 2243 cm(-1), respectively. The N(2)-FTIR experiments performed on the studied catalysts also suggest a lattice plane selectivity for N(2) adsorption on metallic Rh planes of different natures which, to our knowledge, has not been reported yet for Rh.     

Stereoselective synthesis of trifluoromethyl-substituted 1,2-diamines by aza-Michael reaction with trans-3,3,3-trifluoro-1-nitropropene

Aza-Michael addition of optically pure 4-phenyl-2-oxazolidinone to 3,3,3-trifluoro-1-nitropropene proceeds smoothly at low temperature with a high yield. Diastereoselectivity of the addition depends on the base used and lithiated species proved to be highly efficient affording 92% de. Optically pure 1,2-diamino-3,3,3-trifluoropropane is prepared in 58% yield from the aza-Michael addition product through a three-step procedure.