Fast-atom bombardment and tandem mass spectrometry of macrolide antibiotics

Molecular weights of macrolide antibiotics can be determined from either (M + H)⁺ or (M + Met)⁺, the latter desorbed from alkali metal salt-saturated matrices. The ion chemistry of macrolides, as determined by tandem mass spectrometry (MS/MS), is different for ions produced as metallated than those formed as (M + H)⁺ species. An explanation for these differences is the location of the charge. For protonated species, the charge is most likely situated on a functional group with high proton affinity, such as the dimethylamino group of the ammo sugar. The alkali metal ion, however, is bonded to the highly oxygenated aglycone. As a result, the collision-activated dissociation spectra of protonated macrolides are simple with readily identifiable fragment ions in both the high and low mass regions but no fragments in the middle mass range. In contrast, the cationized species give complex spectra with many abundant ions, most of which are located in the high mass range. The complementary nature of the fragmentation of these two species recommends the study of both by MS/MS when determining the structure or confirming the identity of these biomaterials.     

QSAR modeling of flotation collectors using principal components extracted from topological indices

Several topological indices were calculated for substituted-cupferrons that were tested as collectors for the froth flotation of uranium. The principal component analysis (PCA) was used for data reduction. Seven principal components (PC) were found to account for 98.6% of the variance among the computed indices. The principal components thus extracted were used in stepwise regression analyses to construct regression models for the prediction of separation efficiencies (Es) of the collectors. A two-parameter model with a correlation coefficient of 0.889 and a three-parameter model with a correlation coefficient of 0.913 were formed. PCs were found to be better than partition coefficient to form regression equations, and inclusion of an electronic parameter such as Hammett sigma or quantum mechanically derived electronic charges on the chelating atoms did not improve the correlation coefficient significantly. The method was extended to model the separation efficiencies of mercaptobenzothiazoles (MBT) and aminothiophenols (ATP) used in the flotation of lead and zinc ores, respectively. Five principal components were found to explain 99% of the data variability in each series. A three-parameter equation with correlation coefficient of 0.985 and a two-parameter equation with correlation coefficient of 0.926 were obtained for MBT and ATP, respectively. The amenability of separation efficiencies of chelating collectors to QSAR modeling using PCs based on topological indices might lead to the selection of collectors for synthesis and testing from a virtual database.     

Non-equivalence Magnetique en Resonance Nucleaire—IV. Influence de Plusieurs Types de Dissymetries sur les Deplacements Chimiques et les Couplages Relatifs a des Systemes ?O?CH2?CH3 et ?S?CH2?CH3

Magnetic non-equivalence of methylenic protons in A? CH₂? CH₃ groups were studied for several types of compounds. Results are compared with respect (1) to the nature of heteroatom A:A = O and A = S and (2) to the structure of the local dissymmetry element: asymmetric carbon, ketal group and allenic system. Influence of substitution is discussed in relation to conformational problems. Furthermore a variation of the methylene geminal coupling constant with substituents of carbon α to OEt is observed.     

Zirconium complexes having a chiral phosphanylamide in the co-ordination sphere

The chiral phosphanylamido ligand, (N(CHMePh)(PPh2))-, has been introduced into co-ordination chemistry. As starting material the oily amines HN(R-*CHMePh)(PPh2)(1a) and HN(S-*CHMePh)(PPh2)(1b) were used. To reconfirm their absolute structure, 1b was oxidized with H2O2 in air to obtain HN(S-*CHMePh)(P(O)Ph2)(2) as a solid compound. The solid-state structure of 2 was established by single-crystal X-ray diffraction. The lithium salts of both enantiomers Li(N(R-*CHMePh)(PPh2))(3a) and Li(N(S-*CHMePh)(PPh2))(3b) were prepared by deprotonation reaction of 1a,b. Compounds 3a,b were further reacted with zirconocen dichloride to give the chiral metallocenes [(eta5-C5H5)2Zr(Cl)(eta2-N(R-*CHMePh)(PPh2))](4a) and [(eta5-C5H5)2Zr(Cl)(eta2-N(S-*CHMePh)(PPh2))](4b). In an alternative approach to give chiral zirconium compounds, the neutral amine 1b was reacted with [(PhCH2)4Zr] to give the enantiomeric pure complex [(PhCH2)3Zr(eta2-N(S-*CHMePh)(PPh2))](5). The solid-state structures of all zirconium complexes were determined by single-crystal X-ray diffraction.     

Carbaporphyrinoid chemistry has a silver lining! silver(III) oxybenzi-, oxynaphthi-, tropi-, and benzocarbaporphyrins

[structure: see text] Carbaporphyrinoid systems with semiquinone, cycloheptatriene, or indene subunits react under mild conditions with silver(I) acetate to give stable silver(III) organometallic derivatives.     

Early visual evoked potentials are modulated by eye position in humans induced by whole body rotations

Background  

To reach and grasp an object in space on the basis of its image cast on the retina requires different coordinate transformations that take into account gaze and limb positioning. Eye position in the orbit influences the image's conversion from retinotopic (eye-centered) coordinates to an egocentric frame necessary for guiding action. Neuroimaging studies have revealed eye position-dependent activity in extrastriate visual, parietal and frontal areas that is along the visuo-motor pathway. At the earliest vision stage, the role of the primary visual area (V1) in this process remains unclear. We used an experimental design based on pattern-onset visual evoked potentials (VEP) recordings to study the effect of eye position on V1 activity in humans.     

Kinetic approximation of a boundary value problem for conservation laws

Summary. We design numerical schemes for systems of conservation laws with boundary conditions. These schemes are based on relaxation approximations taking the form of discrete BGK models with kinetic boundary conditions. The resulting schemes are Riemann solver free and easily extendable to higher order in time or in space. For scalar equations convergence is proved. We show numerical examples, including solutions of Euler equations.Mathematics Subject Classification (2000): 65M06, 65M12, 76M20Correspondence to: D. Aregba-Driollet     

Optimal design of midsurface of shells: Differentiability proof and sensitivity computation

We suppose that a shell submitted to a given load (self-weight or wind, for instance), has to resist as well as possible towards given criteria. We aim at the following problem: Is it possible to find an optimal design of the midsurface of the shell with respect to this criteria? This problem can be worked using gradient-type algorithms. In this paper we work on the differentiability proof and numerical computation of the gradient. For a given shape of the midsurface, we consider that the shell works in linear elastic conditions. We use the Budiansky-Sanders model for elastic shells, from which we get the displacement field in the shell. The criteria to be minimized are supposed to depend on the shape directly, and also through the displacement field. In this paper, we prove that the displacement field depends on the shape in a Fréchet-differentiable manner (for an appropriate topology on the set of admissible shapes). Then we give a way to compute the gradient of a given criteria from a theoretical point of view and from a numerical point of view. This allows us to use descent-type methods of optimization. They will lead to shapes which react better and better. Notice that we know nothing about convergence of these methods, the existence and unicity of a theoretical optimal solution. But from a practical point of view, it is quite interesting to be able to modify a given shape to obtain a better one.