Untersuchungen über N-Methoxyguanidin 1. Darstellung und spektroskopische Charakterisierung

Studies on N-Methoxyguanidine. 1. Synthesis and Spectroscopic Characterization The hitherto unknown title compound has been isolated as a free base. The infrared, nuclear magnetic resonance, and mass spectra are reported. The amino protones are involved in rapid interchange processes. The activation values of the interchanges have been approximately determined from temperature dependent ¹H-n.m.r. experiments. The related tautomeric structures are discussed.     

Structural data on the packing of poly(ester amide)s derived from glycine,hexanediol, and odd‐numbered dicarboxylic acids

The crystalline structure of a series of Poly(ester amide)s derived from glycine, hexanediol, and odd‐numbered dicarboxylic acids has been studied using transmission electron microscopy and X‐ray diffraction. Polymers crystallize in an orthorhombic lattice with parameters a = 4.80 Å, b = 22.68 Å, and c in the 45–55 Å interval, depending on the number of methylenes of the chemical repeat unit. The structure of the glutaric derivative can be interpreted as a singular packing of six hydrogen‐bonded sheets. Amide and ester interactions between neighboring layers favor two different sheet arrangements that give rise to the observed superstructure. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2521–2533, 1999     

Expanded polyglutamine-binding peptoid as a novel therapeutic agent for treatment of Huntington's disease

Polyglutamine(polyQ)-expanded proteins are potential therapeutic targets for the treatment of polyQ expansion disorders such as Huntington's disease (HD) and spinocerebellar ataxia type 3 (SCA3). Here, we used an amino-terminal fragment of a mutant Huntingtin protein (Htt-N-82Q) as bait in an unbiased screen of a 60,000 peptoid library. Peptoid HQP09 was selected from the isolated hits and confirmed as a specific ligand of Htt-N-82Q and Atxn3-77Q mutant proteins in biochemical experiments. We identified three critical residues in the HQP09 sequence that are important for its activity and generated a minimal?derivative, HQP09_9, which maintains the specific polyQ-binding activity. We demonstrated that HQP09 and HQP09_9 inhibited aggregation of Htt-N-53Q in?vitro and exerted Ca(2+)-stabilizing and neuroprotective effects in experiments with primary striatal neuronal cultures derived from HD mice. We further demonstrated that intracerebroventricular delivery of HQP09 to an HD mouse model resulted in reduced accumulation of mutant Huntingtin aggregates and improved motor behavioral outcomes. These results suggest that HQP09 and similar peptoids hold promise as novel therapeutics for developing treatments for HD, SCA3, and other polyglutamine expansion disorders.     

Photoproduction of η -mesons off protons

Photoproduction of η -mesons was studied with the Crystal-Barrel detector at ELSA for photon energies in the range from 0.75 to 3GeV. Total and differential cross-sections are presented. The η mesons are detected in two decay modes, in η → 2γ and in η → 3π⁰ → 6γ . The cross-sections vary slowly as functions of energy and η production angle suggesting that only few resonances make significant contributions to the cross-section. For photon energies above 1.5GeV, the differential cross-sections show a strong forward peak due to meson exchanges in the t channel. A comparison of the η -photoproduction cross-sections with SAID and MAID as well as with a partial-wave analysis performed on our data in combination with other data sets shows good agreement. The Bonn-Gatchina partial-wave analysis suggests that the largest contribution to η photoproduction for energies below 3GeV proceeds via three resonances, the well-known N(1535)S ₁₁ , via N(1720)P ₁₃ , and a newly suggested N(2070)D ₁₅ .     

Onset of tethered chain overcrowding

We proposed an approach to precisely control the density of tethered chains on solid substrates using PEO-b-PS and PLLA-b-PS. As the crystallization temperature Tx increased, the PEO or PLLA lamellar crystal thickness d(L) increased as well as the reduced tethering density sigma; of the PS chains. The onset of tethered PS chains overcrowding in solution occurs at sigma(*) approximately 3.7-3.8 as evidenced by an abrupt change in the slope between (d(L))(-1) and Tx. This results from the extra surface free energy created by the tethered chain that starts to affect the growth barrier of the crystalline blocks.     

Epitaxial crystallization of isotactic poly(4‐methyl‐pentene‐1)

The crystallization of isotactic poly(4‐methylpentene‐1) in its stable tetragonal crystal modification based on the 7₂ helix conformation was achieved on three different low molecular weight organic substrates and on polytetrafluoroethylene. The contact face was always the (100) face, although the details of the epitaxial relationships generated one, two, or even three chain axis orientations in the polymer epitaxial overgrowth. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3088–3097, 2000     

UNUSUAL CRYSTALLIZATION AND MELTING PROCESSES OF AN OPTICALLY ACTIVE POLYOLEFIN： ISOTACTIC POLY（（S）-4-METHYL-HEXENE-1）

Polyolefins that bear a chiral side chain (typically an isobutyl group) experience a so-called macromolecular amplification of chirality: the chiral side-chain induces a slight preference for either tg or tg- main chain conformation. This slight conformational bias is amplified cooperatively along the chain, and results in preferred chirality of the main chain helical conformations. As a result, these polymers display a liquid-crystal (LC) phase both in solution and, in the melt as a transient phase on the way to crystallization. The existence of two processes (melt-LC and LC-crystal transitions) results in unconventional behaviors that were first analyzed by Pino and collaborators back in 1975. These polymers also offer a means to test the structural consequences of recently introduced crystallization schemes. These schemes postulate the formation of a transient liquid-crystal phase as a general scheme for polymer crystallization.