Coherent Dynamic Structure Factor of a Polymer Chain Confined Into a Harmonic Radial Potential

The coherent dynamic structure factor of a single polymer chain is calculated based on the model of a Rouse polymer chain constrained (confined) by a harmonic radial potential and its behavior in different limiting cases is analyzed. The strength of confinement is characterized using an effective diameter of the harmonic radial potential as a model parameter. The method provides a reliable model to study the crossover between unconstrained (Rouse) and constrained dynamics.

     

Synthesis and structural studies of new N‐(p‐toluenesulfonyl)amino acid o‐phenolamides

N‐(p‐Toluenesulfonyl)glycine o‐phenolamide ( 3a ) and the analogous derivatives of d,l‐alanine ( 3b ), L ‐valine ( 3c ), L ‐leucine ( 3d ), and L ‐phenylalanine ( 3e ) were synthesized in yields >80% by condensation of N‐(p‐toluenesulfonyl)amino acyl chlorides with o‐aminophenol. The structure and conformation of these amides were established by NMR spectroscopy and X‐ray crystallography. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:247–253, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10135     

Stereoselective hydrogenation of methylcyclohex-2-ene-1,4-diols used in the synthesis of ampelomins and deoxy-carbasugars

Stereoselective hydrogenation of methylcyclohex-2-ene-1,4-diols used as important intermediates for the preparation of ampelomins and deoxy-carbasugars was studied. These olefins were obtained in few steps from a chiral cis-diol resulting from microbial oxidation of toluene. Although the stereoselective hydrogenation of this type of substrates is difficult, high yields were obtained for heterogeneous hydrogenation using Adam’s catalyst, where steric hindrance controlled the stereochemical outcome of the process. On the other hand, for homogeneous hydrogenation of similar olefins using Crabtree’s catalyst, coordination with the allylic alcohols allowed for a controlled hydrogen addition from the more hindered face. In this manner two protocols for the hydrogenation of these types of substrates resulting in complementary stereoselectivities are described.     

Triarylcarbinol functionalized gold nanoparticles for the colorimetric detection of nerve agent simulants

Gold nanoparticles functionalized with a triarylcarbinol derivative have been used as colorimetric molecular probes for the naked-eye detection of the nerve agent simulants DCNP and DFP. The detection process is based on the compensation of charges at the surface of the nanoparticles which triggers their aggregation in solution with the resulting change in their plasmon band.     

Stereoselective synthesis of 3-oxygenated-cis-dialkyl-2,5-substituted tetrahydrofurans from cyclohexadienediols

The 3-oxygenated-cis-dialkyl-2,5-substituted tetrahydrofuran system, present in several natural products, was prepared with good selectivity by acidic cyclization of 5-alkene-1,2,4-triol derivatives. The starting alkenol was obtained in few steps from a chiral cis-diol resulting from microbial oxidation of bromobenzene. The study of the cyclization allowed the rationalization of all experimental results by assuming a complete ionization at the allylic position and a model close to the one proposed by Labelle for homoallylic induction in five-membered ring closures.     

Synthesis and crystallographic studies of two new 1,3,5‐triazines

The synthesis and characterization of two new 1,3,5‐triazines containing 2‐(aminomethyl)‐1H‐benzimidazole hydrochloride as a substituent are reported, namely, 2‐{[(4,6‐dichloro‐1,3,5‐triazin‐2‐yl)amino]methyl}‐1H‐benzimidazol‐3‐ium chloride, C₁₁H₉Cl₂N₆⁺·Cl^? ( 1 ), and bis(2,2′‐{[(6‐chloro‐1,3,5‐triazine‐2,4‐diyl)bis(azanediyl)]bis(methylene)}bis(1H‐benzimidazol‐3‐ium)) tetrachloride heptahydrate, 2C₁₉H₁₈ClN₉²⁺·4Cl^?·7H₂O ( 2 ). Both salts were characterized using single‐crystal X‐ray diffraction analysis and IR spectroscopy. Moreover, the NMR (¹H and ¹³C) spectra of 1 were obtained. Salts 1 and 2 have triclinic symmetry (space group P) and their supramolecular structures are stabilized by hydrogen bonding and offset π–π interactions. In hydrated salt 2 , the noncovalent interactions yield pseudo‐nanotubes filled with chloride anions and water molecules, which were modelled in the refinement with substitutional and positional disorder.