Relative and Absolute Configuration of Vatiparol (1 mg): A Novel Anti‐inflammatory Polyphenol

Bioactive natural products offer multiple opportunities for the discovery of novel chemical entities with potential pharmaceutical, nutraceutical and agrochemical applications. Many new organic compounds with novel scaffolds are isolated in small quantities and established methods often fail to determine the structure and bioactivity of such novel natural products. To meet this challenge, we present here a new methodology combining RDC (residual dipolar coupling)‐based NMR spectroscopy in microtubes, with a motif‐inspired biological assessment strategy. Using only one milligram (ca. 1.5 μmol) of sample, the new protocol established the bioactivity as well as the relative and absolute configuration of vatiparol obtained from Vatica parvifolia. Vatiparol is unique in its unprecedented carbon skeleton and selective inhibitory effect on the expression of monocyte chemo‐attractant protein‐1 (MCP‐1, also known as CCL2). The plausible biosynthetic pathway of vatiparol is briefly discussed. The approach introduced here promises to be widely applicable to the determination of the structure and bioactivity of structurally unknown organic samples available in very limited amounts.     

A scheme related to the Brauer loop model

We introduce the Brauer loop scheme, where • is a certain degeneration of the ordinary matrix product. Its components of top dimension, ⌊N²/2⌋, correspond to involutions π∈SN having one or no fixed points. In the case N even, this scheme contains the upper-upper scheme from [A. Knutson, Some schemes related to the commuting variety, J. Algebraic Geom., in press, math.AG/0306275] as a union of (N/2)! of its components. One of those is a degeneration of the commuting variety of pairs of commuting matrices.The Brauer loop model is an integrable stochastic process studied in [J. de Gier, B. Nienhuis, Brauer loops and the commuting variety, J. Stat. Mech. (2005) P01006, math.AG/0410392], based on earlier related work in [M.J. Martins, B. Nienhuis, R. Rietman, An intersecting loop model as a solvable super spin chain, Phys. Rev. Lett. 81 (1998) 504-507, cond-mat/9709051], and some of the entries of its Perron-Frobenius eigenvector were observed (conjecturally) to equal the degrees of the components of the upper-upper scheme.Our proof of this equality follows the program outlined in [P. Di Francesco, P. Zinn-Justin, Inhomogeneous model of crossing loops and multidegrees of some algebraic varieties, math-ph/0412031]. In that paper, the entries of the Perron-Frobenius eigenvector were generalized from numbers to polynomials, which allowed them to be calculated inductively using divided difference operators. We relate these polynomials to the multidegrees of the components of the Brauer loop scheme, defined using an evident torus action on E. As a consequence, we obtain a formula for the degree of the commuting variety, previously calculated up to 4×4 matrices.     

A vibrational CASSCF study of stretch-bend interactions and their influence on infrared intensities in the water molecule

Summary An extension of the multiconfigurational SCF approach for the resolution of the vibrational problem is presented; it follows the philosophy of the CASSCF method developed in Quantum Chemistry. The new method allows a more complete treatment of anharmonic mode couplings, converges much faster and gives a clearer physical insight of vibrational interactions. This is exemplified by the calculation of infrared transition moments in the H₂O and D₂O isotopomers of the water molecule. It is shown how this property varies with the quality of the wave function when vibrational resonances occur. A detailed analysis by means of this new VCASSCF method demonstrates the crucial importance of excited bending oscillators in the intensity of some pure stretching transitions.Boursier F.R.I.A.     

Spatial structure of peptides determined by residual dipolar couplings analysis

The gated decoupled (13)C NMR spectra of a dipeptide (Glu-Trp) and a tetrapeptide (NAc-Ser-Phe-Val-Gly-OMe) were recorded in D(2)O and in a lyotropic alignment medium (pentaethylene glycol monododecyl ether/n-hexanol). The residual dipolar couplings were extracted as the differences between the observed couplings for the magnetic nuclei dissolved in the latter and former media. Using a computational optimization, the spatial structures of the compounds were calculated starting from their respective low energy conformations obtained on a semiempirical basis. The uniformity of each conformation was confirmed by the solid-state (13)C NMR spectra of powder samples. Differences between the starting structures and final ones, optimized when employing residual dipolar couplings, are discussed.     

Central elements of the elliptic monodromy matrix algebra at roots of unity

The central elements of the algebra of monodromy matrices associated with the R-matrix are studied. When the crossing parameter w takes a special rational value , where N and n are positive coprime integers, the center is substantially larger than that in the generic case for which the “quantum determinant” provides the center. In the trigonometric limit, the situation corresponds to the quantum group at roots of unity. This is a higher rank generalization of the recent results by Belavin and Jimbo.     

1H, 13C, 17O NMR and quantum‐chemical study of the stereochemistry of the sulfoxide and sulfone derivatives of 3‐arylidene‐1‐thioflavan‐4‐one epoxides

The oxidation of the trans,cis‐( 2 ) and trans,trans‐epoxides ( 3 ) of differently substituted (Z)‐3‐arylidene‐1‐thioflavan‐4‐ones ( 1 ) with dimethyldioxirane (DMD) yielded the appropriate sulfoxides ( 4, 5 ) and sulfones ( 6, 7 ). The structures were elucidated by the extensive application of one‐ and two‐dimensional ¹H, ¹³C and ¹⁷O NMR spectroscopy. The conformational analysis was achieved by the application of ³J(C,H) coupling constants, NOESY responses and ab initio calculations. The preferred ground‐state conformers (twisted envelope‐A, twisted envelope‐B for 6 and twisted envelope‐A, envelope‐B for 7 ) were obtained as global minima of the theoretical ab initio MO study and also the examination of the ¹⁷O and ¹³C chemical shifts, calculated for the global minima structures of the sulfone isomers by the GIAO method. Analogous results, obtained for the sulfoxide isomers ( 4, 5 ), not only led to the preferred conformers but also gave evidence for the trans arrangement of the 2‐Ph group and the oxygen atom of the S?O group. Chemical shift differences between the isomers, sulfoxides and sulfones were corroborated by ab initio calculations of the anisotropic effects of the oxirane ring and the S?O and SO₂ groups. Copyright © 2003 John Wiley & Sons, Ltd.     

等谱和非等谱TD族,Lax表示与零曲率表示

首先，推广文「１」的结果，建立了等谱和非等谱ＴＤ族，并给出相应的Ｌａｘ表示，再用文「２」的方法得到了相应的零曲率表示。     

(1)H and (13)C NMR studies of asymmetrically substituted bis- and tris-Tröger's bases

The (1)H and (13)C NMR spectra of two stereoisomeric bis-Tr?ger's bases and four stereoisomeric tris-Tr?ger's bases asymmetrically substituted on the external aromatic rings were recorded and the corresponding signals assigned. The relative configuration of the stereogenic units has been unequivocally determined on the basis of homoallylic couplings and NOE experiments.