Conformational selection of glycomimetics at enzyme catalytic sites: experimental demonstration of the binding of distinct high-energy distorted conformations of C-, S-, and O-glycosides by E. Coli beta-galactosidases

We show that the conformational features of the molecular complexes of E. coli beta-galactosidase and O-glycosides may differ from those formed with closely related compounds in their chemical nature, such as C- and S-glycosyl analogues. In the particular case presented here, NMR and ab initio quantum mechanical results show that the 3D-shapes of the ligand/inhibitor within the enzyme binding site depend on the chemical nature of the compounds. In fact, they depend on the relative size of the stereoelectronic barriers for chair deformation or for rotation around Phi glycosidic linkage.     

Efficient synthesis of enantiomerically pure alpha-alkyl cyclopropanecarbonitrile derivatives from pyrazolines

[reaction: see text] Thermolysis of enantiopure sulfonyl pyrazolines 4 and 5, easily obtained from (Z)-3-p-tolylsulfinylacrylonitriles (1), afforded sulfonyl cyclopropanes (6, 7) in a completely stereoselective manner in almost quantitative yields. Both cyclopropanes and alkylidenecyclopropanes, containing one or two chiral carbon atoms, one of them being quaternary, were obtained by hydrogenolysis of the C-S bonding and under the conditions reported by Julia, respectively. The highly stereoselective extrusion of nitrogen suggests a concerted mechanism.     

Lattice invariants and the center of the generic division ring

Let be a finite group, let be a -lattice, and let be a field of characteristic zero containing primitive roots of 1. Let be the quotient field of the group algebra of the abelian group . It is well known that if is quasi-permutation and -faithful, then is stably equivalent to . Let be the center of the division ring of generic matrices over . Let be the symmetric group on symbols. Let be a prime. We show that there exist a split group extension of by a -elementary group, a -faithful quasi-permutation -lattice , and a one-cocycle in such that is stably isomorphic to . This represents a reduction of the problem since we have a quasi-permutation action; however, the twist introduces a new level of complexity. The second result, which is a consequence of the first, is that, if is algebraically closed, there is a group extension of by an abelian -group such that is stably equivalent to the invariants of the Noether setting .

     

Aberro-polariscope for the human eye

We have developed an aberro-polariscope that simultaneously measures spatially resolved polarization properties and wave-front aberration in a living human eye. The setup consists of an infrared Hartmann-Shack sensor that incorporates a polariscope. A series of four Hartmann-Shack images corresponding to independent polarization states were recorded. The corresponding wave-front aberration was computed from each image. Moreover, from each set of four images spatially resolved (over the pupil plane) parameters of polarization were also determined. This instrument allows useful information on both the optical and the biomechanical properties of the eye to be obtained.     

Naphthalene analogues of lignans

The methodology for the synthesis of podophyllotoxin and thuriferic acid-type lignans has been applied to derivatives carrying a naphthalene moiety. Starting from the 1,3-dithiane of 2-naphthaldehyde afforded the expected analogues in the 2,1-naphthalene series. The preferred conformations of these compounds are influenced by the bulky naphthalene system. By contrast, 1,8-bridged products were obtained from the 1,3-dithiane of 1-naphthaldehyde. In this series, polycyclic naphthalene lignan analogues were isolated after deprotection and/or desulfurization reactions. The cyclizations produced in this process are due to the proximity between the 3,4,5-trimethoxyphenyl moiety and the reacting C-2 of the 1,3-dithiane ring.     

Stereodifferentiation of chiral compounds using reversed-phase liquid chromatography coupled with capillary gas chromatography

A method is described for the enantiomeric quantitation of some chiral compounds via online coupling of reversed-phase liquid chromatography-gas chromatography. The evaluation of some variables affecting the experimentation (i.e., the packing material used in the interface, volume of the transferred fraction, desorption time, initial temperature of the interface, and purge time) makes it possible to optimize the recoveries obtained for some chiral terpenes and lactones using a capillary column of beta-cyclodextrin dissolved in OV-1701. The proposed method allows the enantiomeric analysis of aqueous matrices obtaining relative standard deviations lower than 9% and detection limits ranging from 0.26-0.93 ppm for the investigated compounds.     

Hermite Interpolation and Sobolev Orthogonality

In this paper, we study orthogonal polynomials with respect to the bilinear form (f, g) _S = V(f) A V(g) ^T + <u, f ^(N) g ^(N)V(f) =(f(c ₀), f "(c ₀), ..., f ^{(n – 1)} ₀(c ₀), ..., f(c _p ), f "(c _p ), ..., f ^{(n – 1)} _p(c _p )) u is a regular linear functional on the linear space P of real polynomials, c ₀, c ₁, ..., c _p are distinct real numbers, n ₀, n ₁, ..., n _p are positive integer numbers, N=n ₀+n ₁+...+n _p , and A is a N × N real matrix with all its principal submatrices nonsingular. We establish relations with the theory of interpolation and approximation.     

2-Aryl-7,7-dimethyl-5,6,7,8-tetrahydrothieno[3,2-c]azepin-4-ones from 5,5-dimethyl-1,3-cyclohexanedione

A novel synthesis of substituted thieno[3,2-c]azepinones is described. This new approach uses 5,5-dimethyl-1,3-cyclohexanedione (dimedone) as the starting material. Oxime intermediates are obtained in three steps from the aforementioned diketone. Using these intermediates, the title compounds are synthesized in moderate yields.     

On the performance of the ICP algorithm

We present upper and lower bounds for the number of iterations performed by the Iterative Closest Point (ICP) algorithm. This algorithm has been proposed by Besl and McKay as a successful heuristic for matching of point sets in d-space under translation, but so far it seems not to have been rigorously analyzed. We consider two standard measures of resemblance that the algorithm attempts to optimize: The RMS (root mean squared distance) and the (one-sided) Hausdorff distance. We show that in both cases the number of iterations performed by the algorithm is polynomial in the number of input points. In particular, this bound is quadratic in the one-dimensional problem, under the RMS measure, for which we present a lower bound construction of Ω(nlogn) iterations, where n is the overall size of the input. Under the Hausdorff measure, this bound is only O(n) for input point sets whose spread is polynomial in n, and this is tight in the worst case.We also present several structural geometric properties of the algorithm under both measures. For the RMS measure, we show that at each iteration of the algorithm the cost function monotonically and strictly decreases along the vector Δt of the relative translation. As a result, we conclude that the polygonal path π, obtained by concatenating all the relative translations that are computed during the execution of the algorithm, does not intersect itself. In particular, in the one-dimensional problem all the relative translations of the ICP algorithm are in the same (left or right) direction. For the Hausdorff measure, some of these properties continue to hold (such as monotonicity in one dimension), whereas others do not.