Renewable-resource thermoplastic elastomers based on polylactide and polymenthide

An alpha,omega-functionalized polymenthide was synthesized by the ring-opening polymerization of menthide in the presence of diethylene glycol with diethyl zinc as the catalyst. Termination with water afforded the dihydroxy polymenthide. The reaction of this telechelic polymer with triethylaluminum formed the corresponding aluminum alkoxide macroinitiator that was used for the controlled polymerization of lactide to yield biorenewable polylactide-b-polymenthide-b-polylactide triblock copolymers. The molecular weight and chemical composition were easily adjusted by the monomer-to-initiator ratios. Microphase separation in these triblock copolymers was confirmed by small-angle X-ray scattering and differential scanning calorimetry. A representative triblock was prepared with a hexagonally packed cylindrical morphology as determined by small-angle X-ray scattering, and tensile testing was employed to assess the mechanical behavior. On the basis of the ultimate elongations and elastic recovery, these triblock copolymers behaved as thermoplastic elastomers.     

2'-Nor-cGMP: a seco-cyclic nucleotide with powerful anti-DNA-viral activity

As part of our study of antiherpetic acyclonucleosides, we synthesized a cyclic GMP analog, 9-[(2-hydroxy-1,3,2-dioxaphosphorinan-5-yl)oxymethyl]guanine P-oxide, sodium salt (2'-nor-cGMP), and discovered its potent and broad spectrum anti-DNA-viral activities. 2'-Nor-cGMP inhibits the replication of many DNA viruses, including herpes simplex virus, human cytomegalovirus, vaccinia, SV40, and adenovirus, but does not inhibit RNA viruses. In plaque reduction studies this potent antiviral agent is also approximately 10-fold more potent than 9-(1,3-dihydroxy-2-propoxymethyl)guanine (2'NDG) against varicella-zoster virus and inhibits cell transformation by bovine papilloma virus. Unlike 2'NDG, the potent activity of 2'-nor-cGMP against herpes virus is not dependent upon the action of virus-specified thymidine kinase. Intercellular metabolism of 2'-nor-cGMP produced small amounts of 2'NDG triphosphate which were insufficient to account for the antiviral activity observed, implying that this potent anti-DNA-viral agent operates by a mechanism different from that of known acyclonucleosides.     

Type 1 copper site synthetic model complexes with increased redox potentials

Reactions of NaSCPh₃ with (R₃tacn)Cu(OTf)₂ (R is Me, iPr; tacn is 1,4,7-triazacyclononane; OTf is CF₃SO₃ ⁻) yield blue complexes identified as ((R₃tacn)CuSCPh₃)(OTf) on the basis of UV–vis, resonance Raman, and electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization mass spectrometry. These complexes exhibit spectroscopic properties typical of type 1 copper sites in proteins, including diagnostic Sπ → Cu(d_{x² - y²} ) (d_{{x^{2} - y^{2} }} ) ligand-to-metal charge transfer transitions at approximately 610–630 nm and small A _|| values in EPR spectra of less than 100 × 10⁻⁴ cm⁻¹. Cyclic voltammetry experiments revealed redox potentials for the complexes similar to those of several low-potential type 1 copper proteins (e.g., azurin, stellacyanin) and approximately 0.5 V higher than those of previously reported model compounds. Thus, the new complexes mimic key aspects of both the structure and the function of type 1 copper sites.