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161.
Daniele Balducci Simone Contaldi Ilaria Lazzari Gianni Porzi 《Tetrahedron: Asymmetry》2009,20(12):1398-1401
A new, practical and very convenient stereocontrolled synthesis of (S)-2′,6′-dimethyltyrosine [(S)-Dmt] 4 was accomplished in a good yield, starting from the chiral synthon 1,4-N,N-[(S)-phenylethyl]-piperazine-2,5-dione 1. The procedure, which is an extension of our original strategy and occurs with a high level of stereoselectivity (>98%), is simple and inexpensive allowing us to prepare the unnatural α-aminoacid (S)-Dmt also on a multi-gram scale. 相似文献
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The parameter mixing rules of the Soave–Redlich–Kwong (SRK) equation of state are rewritten as Huron–Vidal mixing rules, where infinite-pressure activity coefficients are predicted by group contributions. Alkanes are treated as composed by one group type and aromatics by two types, aliphatic and aromatic. Hydrocarbon mixtures can be treated using one universal interaction parameter. Light compounds like methane, N2, CO2, H2S, etc. are treated as separate groups; each one requires a pair of parameters for its interactions with aliphatic and aromatic groups. Group interaction parameters were determined from experimental VLE data. From them, binary interaction constants of the classical quadratic mixing rules can directly be derived. 相似文献
165.
Control of degradation of polypropylene during its radical functionalisation with furan and thiophene derivatives 总被引:2,自引:0,他引:2
The traditional melt radical functionalisation of isotactic polypropylene (iPP) with maleic anhydride (MAH) and peroxide affords functionalized samples with a severe decrease of the average molecular weight (MW) due to the β-scission reaction. In this work new push-pull unsaturated molecules were investigated, consisting of a heterocyclic ring conjugated with a double bond bearing an electron attracting group. These molecules were specifically designed as MAH substitute able to limit the iPP degradation, while providing functionalisation through grafting. Butyl 3-(2-furanyl) propenoate (BFA) and butyl 3-(2-thienyl) propenoate (BTA) were comparatively tested. The analysis of the reaction products indicated that both molecules are able to graft onto the iPP backbone by prompt reaction with the macro-radicals formed through H-abstraction from iPP chains, thereby significantly limiting the MW decrease, as the functionalized macro-radicals are stabilized by resonance. Nonetheless, some of iPP macro-radicals can give a parallel chain scission before reacting with the new molecules. In the case of BFA, coupling reactions of the formed macro-radicals can lead to the formation of branched high MW architectures, whereas in the case of the thiophene derivative (BTA) only a partial retaining of polymer chain fragmentation was observed due to the reduction of β-scission. 相似文献
166.
Carlo Bertucci Marco Pistolozzi Angela De Simone 《Analytical and bioanalytical chemistry》2010,398(1):155-166
Chirality plays a fundamental role in determining the pharmacodynamic and pharmacokinetic properties of drugs, and contributes significantly to our understanding of the mechanisms that lie behind biorecognition phenomena. Circular dichroism spectroscopy is the technique of choice for determining the stereochemistry of chiral drugs and proteins, and for monitoring and characterizing molecular recognition phenomena in solution. The role of chirality in our understanding of recognition phenomena at the molecular level is discussed here via several selected systems of interest in the drug discovery and development area. The examples were selected in order to underline the utility of circular dichroism in emerging studies of protein–protein interactions in biological context. In particular, the following aspects are discussed here: the relationship between stereochemistry and pharmacological activity—stereochemical characterization of new leads and drugs; stereoselective binding of leads and drugs to target proteins—the binding of drugs to serum albumins; conformational transitions of peptides and proteins of physiological relevance, and the stereochemical characterization of therapeutic peptides. 相似文献
167.
Dawei Jiang Simone Budow Virginie Glaon Henning Eickmeier Hans Reuter Yang He Frank Seela 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(4):o194-o197
The title compound, C10H12FN5O4·H2O, shows an anti glycosyl orientation [χ = −123.1 (2)°]. The 2‐deoxy‐2‐fluoroarabinofuranosyl moiety exhibits a major C2′‐endo sugar puckering (S‐type, C2′‐endo–C1′‐exo, 2T1), with P = 156.9 (2)° and τm = 36.8 (1)°, while in solution a predominantly N conformation of the sugar moiety is observed. The conformation around the exocyclic C4′—C5′ bond is −sc (trans, gauche), with γ = −78.3 (2)°. Both nucleoside and solvent molecules participate in the formation of a three‐dimensional hydrogen‐bonding pattern via intermolecular N—H...O and O—H...O hydrogen bonds; the N atoms of the heterocyclic moiety and the F substituent do not take part in hydrogen bonding. 相似文献
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169.
Riccardo March Giovanni Bellettini Roberto Tauraso Simone Dell’Agnello 《General Relativity and Gravitation》2011,43(11):3099-3126
We compute the corrections to the orbital Lense-Thirring effect (or frame-dragging) in the presence of spacetime torsion.
We analyze the motion of a test body in the gravitational field of a rotating axisymmetric massive body, using the parametrized
framework of Mao, Tegmark, Guth and Cabi. In the cases of autoparallel and extremal trajectories, we derive the specific approximate
expression of the corresponding system of ordinary differential equations, which are then solved with methods of Celestial
Mechanics. We calculate the secular variations of the longitudes of the node and of the pericenter. We also show how the LAser
GEOdynamics Satellites (LAGEOS) can be used to constrain torsion parameters. We report the experimental constraints obtained
using both the nodes and perigee measurements of the orbital Lense-Thirring effect. This makes LAGEOS and Gravity Probe B
complementary frame-dragging and torsion experiments, since they constrain three different combinations of torsion parameters. 相似文献
170.