Toward partial fucosyl transferase transition state analogues: methylene sulfono sulfonamide as surrogate of pyrophosphate

Partial fucosyl transferase transition state analogues having sulfonoacetamido- and methylene sulfono sulfonamide links as a non-charged surrogate of the pyrophosphate moiety have been prepared from fructose and guanosine. The use of a MOM group at N1 and a formamidine group at the primary amine function for the protection of the guanine residue proved troublesome.     

A propos de l'espace des modules de fibrés de rang 2 sur une courbe

Sans résumé

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Partiellement financé par le contrat Science Geometry of Algebraic Varieties, contrat n^o SCI-0398-C     

The Value of Advance Demand Information in Production/Inventory Systems

Advance demand information, when used effectively, improves the performance of production/inventory systems. In this paper, we investigate the value of advance demand information in production/inventory systems. For a single-stage make-to-stock queue, we assess the value of using advance demand information under a variety of assumptions on the cost of obtaining advance demand information, and the delivery timing requirements. This analysis enables us to identify conditions under which advance demand information may bring significant benefits.     

SPIN-TRAPPING and ESR STUDIES OF THE DIRECT PHOTOLYSIS OF AROMATIC AMINO ACIDS, DIPEPTIDES, TRIPEPTIDES and POLYPEPTIDES IN AQUEOUS SOLUTIONS—III. TRYPTOPHAN and RELATED COMPOUNDS

Abstract— The UV photolysis of tryptophan (Trp) and Trp-containing peptides in aerated aqueous solutions has been studied by ESR and spin-trapping techniques using f-nitrosobutane as the spin-trap. The photolysis of Trp alone at 290 nm gave rise to the addition of the spin-trap to carbon 3 of the indole ring. A large ESR signal from the hydronitroxide spin-adduct was also observed revealing the formation of hydrated electrons. Generally, the photolysis of Trp-containing dipeptides generated the deamination radical of the N-terminal amino acid followed by addition to the spin-trap. In the case of lysyl-Trp, a deamination radical from the side chain of lysine was proposed. A sensitization experiment with Trp as sensitizer and glycine (Gly) as substrate led to the generation of the deamination radical of Gly. Most of the observed free radicals resulting from the photolysis of Trp-containing peptides can be explained in terms of hydrated electrons reacting with the carbonyl group followed by deamination of the N-terminus.     

Experimental and numerical study of entry flow of low-density polyethylene melts

The present work deals with experimental and numerical features of entry flows of two polyethylene melts, namely a linear low-density polyethylene (LLDPE) and a low-density polyethylene (LDPE) in an axisymmetric converging geometry. The study also involves rheological characterization of the polymers and determination of flow parameters, at 160°C. For both fluids, the data are fed into a viscoelastic integral Wagner constitutive equation. The numerical flow simulations are performed by using a stream-tube mapping analysis. Consideration of a sub-domain of the total flow domain, the peripheral stream tube, close to the wall of the converging duct permits to relate the results of the numerical simulation to experimental flow characteristics as total and entrance pressure drops. The agreement is good for the total pressure losses, but, concerning LDPE, a lack of consistency remains for the entrance pressure drop.     

Synthesis of the sulfones of leukotriene C4, D4, and E4

A simple one-step preparation of the sulfones of Leukotriene C₄, D₄ and E₄ has been developed by the direct oxidation of the parent compounds. An alternative synthesis of these sulfones has also been carried out by reduction of an acetylenic precursor.     

Gas-phase bimolecular reactions between (.)CH(2)-(CH(2))(n)-C(+)=O distonic ions and pyridine: a combined experimental and theoretical study

The gas-phase reactivities of the well-known (.)CH(2)CH(2)C(+)=O and (.)CH(2)CH(2)CH(2)C(+)=O distonic ions towards neutral pyridine were studied both experimentally (six sector hybrid mass spectrometer) and theoretically (density functional theory and M?ller-Plesset ab initio calculations). Competitively to the charge exchange and protonation processes, both radical cations react with pyridine by an initial bonding between the positive charge site of the ion and the lone electron pair of the neutral molecule. At variance with previously reported studies in which such a nucleophilic interaction was proposed to play only a transient catalytic role, the initial C-N bond is likely to remain in the observed ion-molecule reaction products. The structures of the ion-molecule reactions products were probed by collisional activation at high kinetic energy and the reaction pathways were tentatively proposed on the basis of labeling experiments and ab initio molecular orbital calculations.     

Analysis of the half-projected Hartree–Fock function: Density matrix,natural orbitals,and configuration interaction equivalence

The half-projected Hartree–Fock function for singlet states (HPHF ) is analysed in terms of natural electronic configurations. For this purpose the HPHF spinless density matrix and its natural orbitals are first deduced. It is found that the HPHF function does not contain any contribution from odd-times excited configurations. It is seen in addition, in the case of the singlet ground states, this function is approximately equivalent to two closed-shell configurations, although the nature of the excited one depends on the nuclear geometry. An example is given in the case of the LiH ground state. Finally, the application of this model for studying systems of more that two atoms is criticized.     

Electrochemical behavior of the tris(pyridine)-Cu funnel complexes: an overall induced-fit process involving an entatic state through a supramolecular stress

The electrochemical behavior of the tris(pyridine) calix[6]arene Cu adducts is unique as compared to that of most classical Cu complexes in a strain-free environment. The presence of MeCN buried inside the cavity is a prerequisite for a quasi-reversible behavior in a dynamic mode. The CV behavior assisted by simulation outlines that the coordination adaptability of the Cu(II)/Cu(I) redox states is completely reversed, with a Td geometry enforced at either redox states. Hence, the supramolecular control of the Cu coordination by a protein-like pocket determines the dynamics of the electron transfer process, its thermodynamics, and the kinetics of the reorganizational barrier and generates a preorganized state for oxidation. This redox behavior corresponds to an overall induced-fit process generating a truly entatic highly oxidizing Cu(II) state through a protein-like strain by involvement of the secondary coordination sphere.