Determination of sugar structures in solution from residual dipolar coupling constants: methodology and application to methyl beta-D-xylopyranoside

We have developed methodology for the determination of solution structures of small molecules from residual dipolar coupling constants measured in dilute liquid crystals. The power of the new technique is demonstrated by the determination of the structure of methyl beta-d-xylopyranoside (I) in solution. An oriented sample of I was prepared using a mixture of C(12)E(5) and hexanol in D(2)O. Thirty residual dipolar coupling constants, ranging from -6.44 to 4.99 Hz, were measured using intensity-based J-modulated NMR techniques. These include 15 D(HH), 4 (1)D(CH), and 11 (n)D(CH) coupling constants. The accuracy of the dipolar coupling constants is estimated to be < +/- 0.02 Hz. New constant-time HMBC NMR experiments were developed for the measurement of (n)D(CH) coupling constants, the use of which was crucial for the successful structure determination of I, as they allowed us to increase the number of fitted parameters. The structure of I was refined using a model in which the directly bonded interatom distances were fixed at their ab initio values, while 16 geometrical and 5 order parameters were optimized. These included 2 CCC and 6 CCH angles, and 2 CCCC and 6 CCCH dihedral angles. Vibrationally averaged dipolar coupling constants were used during the refinement. The refined solution structure of I is very similar to that obtained by ab initio calculations, with 11 bond and dihedral angles differing by 0.8 degrees or less and the remaining 5 parameters differing by up to 3.3 degrees . Comparison with the neutron diffraction structure showed larger differences attributable to crystal packing effects. Reducing the degree of order by using dilute liquid crystalline media in combination with precise measurement of small residual dipolar coupling constants, as shown here, is a way of overcoming the limitation of strongly orienting liquid crystals associated with the complexity of (1)H NMR spectra for molecules with more than 12 protons.     

Effects of thioamide substitutions on the conformation and stability of alpha- and 3(10)-helices

Thiopeptides, formed by replacing the amide oxygen atom with a sp(2) sulfur atom, are useful in protein engineering and drug design because they confer resistance to enzymatic degradation and are predicted to be more rigid. This report describes our free molecular dynamics simulations with explicit water and free energy calculations on the effects of thio substitutions on the conformation of alpha-helices, 3(10)-helices, and their relative stability. The most prominent structural effect of thio substitution is the increase in the hydrogen bond distance from 2.1 A for normal peptides to 2.7 A for thiopeptides. To accommodate for the longer C[double bond]S...H-N hydrogen bond, the (phi, psi) dihedral angles of the alpha-helix changed from (-66 degrees, -42 degrees) to (-68 degrees, -38 degrees), and the rise per turn increased from 5.5 to 6.3 A. For 3(10)-helices, the (phi, psi) dihedral angles (-60 degrees, -20 degrees) and rise per turn (6.0 A) changed to (-66 degrees, -12 degrees) and 6.8 A, respectively. In terms of relative stability, the most prominent change upon thio substitution is the decrease in the free energy difference, Delta A(alpha --> 3(10)), from 14 to 3.5 kcal/mol. Therefore, normal peptides are less likely to form 3(10)-helix than are thiopeptides. Component analysis of the Delta A(alpha --> 3(10)) reviews that the entropy advantage of the 3(10)-helix for both Ac-Ala(10)-NHMe and Act-Alat(10)-NHMe is attributed to the 3(10)-helix being more flexible than the alpha-helix. Interestingly, upon thio substitution, this differential flexibility is even more apparent because the alpha-helix conformation of Act-Alat(10)-NHMe becomes more rigid due to the bulkier sulfur atom.     

Wild ginseng grows in Myanmar

Ginseng, the underground parts of plants of Panax species, has been used in oriental traditional medicine for centuries. Unfortunately, because of extensive exploitation over thousands of years, the natural source of these species has been almost exhausted. Recently, we have found a wild ginseng growing in Myanmar. Here, by a combination of chemical composition study and gene sequence analysis, we unambiguously demonstrate that the wild ginseng is actually P. zingiberensis, commonly known as ginger ginseng. This ginseng was an indigenous to the southwestern China. However, now it is seriously threatened to brink of extinction and is put on the highest level of protection in China. Therefore, an appropriate protection measure is highly recommended to preserve this valuable resource, since this Myanmar ginseng might turn out to be the last P. zingiberensis, which could ever be seen in the planet.     

Link between the kinetic‐ and exchange‐energy functionals in the generalized gradient approximation

An approximate kinetic‐energy functional of the generalized gradient approximation form was derived following the “conjointness conjecture” of Lee, Lee, and Parr. The functional shares the analytical form of its gradient dependency with the exchange‐energy functionals of Becke and Perdew, Burke, and Ernzerhof. The two free parameters of this functional were determined using the exact values of the kinetic energy of He and Xe atoms. A set of 12 closed‐shell atoms was used to test the accuracy of the proposed functional and more than 30 others taken from the literature. It is shown that the conjointness conjecture leads to a very good class of kinetic‐energy functionals. Moreover, the functional developed in this work is shown to be one of the most accurate despite its simple analytical form. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Nouvelle méthode de détermination des taux de réativité des copolymères par résonance magnétique nucléaire: Application aux poly(méthacrylate de méthyle–chlorure de vinylidène)

Constant-composition copolymers of methyl methacrylate and vinylidene chloride produced by radical copolymerization are studied by ¹H-NMR at 60 and 250 MHz. The different methods of the literature for the derivation of reactivity ratios from either the copolymer composition or the sequence average lengths, or even the diad distribution, are applied but lead to rather dispersed results. A new graphical method is proposed, based on the use of peculiar values of the triad distribution functions. It allows us to detect a penultimate effect for the vinylidene chloride-rich region. In the same range, a change in tacticity of the diads and triads on the methylmethacrylate sequences, as compared with homopolymers, is observed; it suggests that the anomaly is caused by the competition of the depropagation reaction.     

Polymérisation anionique de l'isoprène: Nature de la paire d'ions et stéréospécificité

With accumulated HR-NMR spectra of anionic polyisoprenes, it has been possible to study the influence of the nature of the propagating species on the microstructure of the obtained polymers If free ions are responsible for the propagation, the microstructure (1,4-: 25%, 1,2-: 33%, 3,4-: 42%) does not depend on the nature of the cations. But with contact ion pairs, the different addition modes are governed by the size of the alkali metal counterions. Mechanisms of anionic propagations via diene–cation coordination are proposed.     

3-Dimethylarsino-propylamin, (CH3)2As?(CH2)3?NH2, und Bis-[3-amino-propyl]-methylarsan,CH3As[(CH2)3?NH2]2

3-Dimethylarsino-propylamine, (CH₃)₂As? (CH₂)₃? NH₂, and Bis-[3-aminopropyl]-methylarsane, CH₃As[(CH₂)₃? NH₂]₂ The reduction of the nitriles Me₂As(CH₂)₂? CN (Me?CH₃) and MeAs(CH₂CH₂? CN)₂ results in the formation of the arsines Me₂As(CH₂)₃? NH₂ and MeAs[(CH₂)₃? NH₂]₂, respectively. The reactivity of these compounds, especially the formation of carbonyl complexes and heterocyclic compounds are described.     

An application of the phosphine-catalyzed [4 + 2] annulation in indole alkaloid synthesis: formal syntheses of (+/-)-alstonerine and (+/-)-macroline

[reaction: see text] An application of the phosphine-catalyzed [4 + 2] annulation in the formal synthesis of alstonerine and macroline is reported. A phosphine-catalyzed [4 + 2] reaction between imine 7a and allene 8 formed the D ring of the target indole alkaloids. A subsequent intramolecular Friedel-Crafts acylation provided the C ring of the bridged tetracycle. Deprotection, followed by methylation of the bridged nitrogen, deoxygenation of the C6 ketone, and reduction of the C16 carbethoxy group provided the previously known intermediate 3.     

Chloration d'un polyethylene ramifie influence de la temperature et du solvant

The chlorination of branched high-pressure polyethylenes, promoted by u.v. at various temperatures in carbon tetrachloride and 1,1–2,2 tetrachloroethane, has been studied. It has been possible to elucidate the influence of the temperature and the nature of the solvent on the characteristics of the chlorinated polymers.The chlorination is more efficient in carbon tetrachloride, where the efficiency of the u.v. is not affected by the medium.At the same degree of chlorination, the chain-breaking mechanisms are more important in carbon tetrachloride than in tetrachloroethane; they increase when the temperature of the medium increases. The chlorine-saturated polyethylene obtained in carbon tetrachloride is richer in 1,2 dichloroethylene sequences.Below 60°, the yield of chlorinated polymer is the same in the two solvents. Chlorination at higher temperature in tetrachloroethane does not improve the structural regularity or the yield of the chlorine-saturated polyethylenes.