Hyperpolarization of 13C through order transfer from parahydrogen: a new contrast agent for MRI

The order within proton pairs in organic molecules, resulting from hydrogenation with parahydrogen, can be transferred in great part to nearby carbon 13 spins through adequate field manipulations. The molecules with hyperpolarized 13C thus obtained can be used as new contrast agents of high efficiency in MRI. After a brief presentation of the hydrogenation process and apparatus, in relatively low magnetic field, we describe the procedure of order transfer to the 13C spins through a sudden drop from the initial field to zero field followed by an adiabatic remagnetization. The expected final polarizations in the absence of relaxation are given for several compounds. Finally, we show an example of MR images observed in vivo on animals as an illustration of the contrast capacity of this new method.     

Mechanistic studies of the transfer dehydrogenation of cyclooctane catalyzed by iridium bis(phosphinite) p-XPCP pincer complexes

Reaction of bis(phosphinite) PCP iridium pincer complexes (p-XPCP)IrHCl (5a-f) [X = MeO (5a), Me (5b), H (5c), F (5d), C(6)F(5) (5e), Ar(F)(= 3,5-bis(trifluoromethyl)phenyl) (5f)] with NaOtBu in neat cyclooctane (COA) generates 1:1 mixtures of the respective (p-XPCP)IrH(2) complexes 4a-f and the cyclooctene (COE) olefin complexes (p-XPCP)Ir(COE) (6a-f) at 23 degrees C. At higher temperatures, complexes 4 and 6 are equilibrated because of the degenerate transfer dehydrogenation of COA with free COE (6 + COA right harpoon over left harpoon 4 + 2COE), as was shown by temperature-dependent equilibrium constants and spin saturation transfer experiments at 80 degrees C. At this temperature, the COE complexes 6 exchange with free COE on the NMR time scale with the more electron-deficient complexes 6 exchanging COE faster. The exchange is dissociative and zero order in [COE]. Further analysis reveals that the stoichiometric hydrogenation of COE by complex 4f, and thus the separated back reaction 4f + 2COE --> 6f + COA proceeds at temperatures as low as -100 degrees C with the intermediacy of two isomeric complexes (p-Ar(F)PCP)Ir(H)(2)(COE) (8f, 8f'). COE deuteration with the perdeuterated complex 4f-d(38) at -100 degrees C results in hydrogen incorporation into the hydridic sites of complexes 8f,8f'-d(38) but not in the hydridic sites of complex 4f-d(38), thus rendering COE migratory insertion in complexes 8f,8f' reversible and COE coordination by complex 4f rate-determining for the overall COE deuteration.     

Weighted allocation rules for standard fixed tree games

In this paper we consider standard fixed tree games, for which each vertex unequal to the root is inhabited by exactly one player. We present two weighted allocation rules, the weighted down-home allocation and the weighted neighbour-home allocation, both inspired by the painting story in Maschler et al. (1995) . We show, in a constructive way, that the core equals both the set of weighted down-home allocations and the set of weighted neighbour allocations. Since every weighted down-home allocation specifies a weighted Shapley value (Kalai and Samet (1988)) in a natural way, and vice versa, our results provide an alternative proof of the fact that the core of a standard fixed tree game equals the set of weighted Shapley values. The class of weighted neighbour allocations is a generalization of the nucleolus, in the sense that the latter is in this class as the special member where players have all equal weights.     

Adjustable cavity for host-guest recognition in cofacial bis-porphyrinic tweezer

The synthesis of a cofacial bis-porphyrinic tweezer bearing a tris-anthracenic spacer is reported. Its behavior as host has been evidenced as well as the ability of its cavity to adjust to guests of various sizes.     

A supramolecular cup-and-ball C60-porphyrin conjugate system

In addition to the ammonium-crown ether recognition, pi-stacking interactions between the C60 sphere and the porphyrin moiety have been evidenced in a supramolecular complex obtained from a porphyrin-crown ether conjugate and a fullerene derivative bearing an ammonium unit.     

Donor-substituted peralkynylated "radiaannulenes": novel all-carbon macrocycles with an intense intramolecular charge-transfer

A novel class of planar, highly conjugated all-carbon macrocycles, which we christened "radiaannulenes", have been prepared based on acetylenic scaffolding using tetraethynylethene (TEE) building blocks; these structures are powerful electron acceptors and, upon peripheral substitution with electron-donating N,N-dialkylanilino groups, display intense intramolecular charge-transfer.     

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.     

Investigation of 3-D mechanical properties of blood vessels using a new in vitro tests system: results on sheep common carotid arteries

In order to investigate the three-dimensional (3-D) mechanical properties of blood vessels, a new experimental device is described allowing in vitro static and dynamic measurements on segments of arteries with high technical performances. Static tests are applied to sheep common carotid arteries. Considering a thick-walled cylindrical model of orthotropic material under large deformations, a classical 3-D approach based on strain energy density is used to calculate the resulting mechanical behavior law in radial and circumferencial directions and stresses distribution throughout the wall thickness. Results are presented with reference to unloaded and zero-stress initial state thanks to simple measurements of inner and outer circumferences. A particular ratio relating the two main stresses (circumferential and longitudinal) is calculated that put into the forth the progressive modifications in the direction of the predominant stress in the wall and the specific radial location where these changes occur. The authors observe that this point location is a function of the test conditions of the specimen, i.e., stretching length and level of pressure     

Equitable resolvable coverings

In an earlier article, Willem H. Haemers has determined the minimum number of parallel classes in a resolvable 2‐(qk,k,1) covering for all k ≥ 2 and q = 2 or 3. Here, we complete the case q = 4, by construction of the desired coverings using the method of simulated annealing. Secondly, we look at equitable resolvable 2‐(qk,k,1) coverings. These are resolvable coverings which have the additional property that every pair of points is covered at most twice. We show that these coverings satisfy k < 2q ? , and we give several examples. In one of these examples, k > q. © 2003 Wiley Periodicals, Inc. J Combin Designs 11: 113–123, 2003; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10024     

Initial stages of oxidation of Cu(1 1 1)

Several surface analysis techniques were combined to study the initial stages of oxidation of Cu(1 1 1) surfaces exposed to O₂ at low pressure (<5 × 10⁻⁶ mbar) and room temperature. Scanning tunneling microscopy (STM) results show that the reactivity is governed by the restructuring of the Cu(1 1 1) surface. On the terraces, oxygen dissociative adsorption leads to the formation of isolated O adatoms and clusters weakly bound to the surface. The O adatoms are located in the fcc threefold hollow sites of the unrestructured terraces. Friedel oscillations with an amplitude lower than 5 pm have been measured around the adatoms. At step edges, surface restructuring is initiated and leads to the nucleation and growth of a two-dimensional disordered layer of oxide precursor. The electronic structure of this oxide layer is characterised by a band gap measured by scanning tunneling spectroscopy to be ∼1.5 eV wide. The growth of the oxide islands progresses by consumption of the upper metal terraces to form triangular indents. The extraction of the Cu atoms at this interface generates a preferential orientation of the interface along the close-packed directions of the metal. A second growth front corresponds to the step edges of the oxide islands and progresses above the lower metal terraces. This is where the excess Cu atoms extracted at the first growth front are incorporated. STM shows that the growing disordered oxide layer consists of units of hexagonal structure with a first nearest neighbour distance characteristic of a relaxed Cu-Cu distance (∼0.3 nm), consistent with local Cu₂O(1 1 1)-like elements. Exposure at 300 °C is necessary to form an ordered two-dimensional layer of oxide precursor. It forms the so-called “29” superstructure assigned to a periodic distorted Cu₂O(1 1 1)-like structure.