Polymeric materials

Summary The Polymer Section of the Santa Barbara Workshop on Modeling of Materials is briefly reviewed. Motivation and need for modeling in polymer-based materials are outlined and the recommendations resulting from the workshop reported.     

Molecular basis and species specificity of high affinity binding of vasoactive intestinal polypeptide by the rat secretin receptor

The affinity and specificity of the binding interaction between ligands and their receptors are key for appropriate hormonal regulation of target tissues. However, it is now apparent that vasoactive intestinal polypeptide (VIP) binds to the rat secretin receptor with similar affinity to that for its natural ligand, secretin (Holtmann et al., 1995). In this report, we establish that this is not a characteristic of the human secretin receptor, and use rat-human secretin receptor chimeras, site mutants and truncated receptor constructs to establish the molecular basis for this unusual binding interaction. Of note, isolated N-terminal domains of the rat secretin and the VIP receptors are capable of high affinity binding of VIP. In the recently recognized secretin family of receptors, this domain has six conserved cysteine residues and disulfide bonds that are likely important to achieve the complex conformation critical for this binding. A single acidic residue (Asp98) present in the rat secretin receptor appears to be critical, because a site-mutant changing this to the polar, but uncharged residue present in that position in the human receptor (Asn) eliminates the high affinity binding of VIP. Of interest, a previously identified critical basic residue in VIP (Lys15) provides a candidate for charge-pairing with this residue, potentially aligning the peptide ligand in a nonproductive orientation within this receptor.     

Polycyclic Aromatic Hydrocarbons Activate the Aryl Hydrocarbon Receptor and the Constitutive Androstane Receptor to Regulate Xenobiotic Metabolism in Human Liver Cells

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants produced by incomplete combustion of organic matter. They induce their own metabolism by upregulating xenobiotic-metabolizing enzymes such as cytochrome P450 monooxygenase 1A1 (CYP1A1) by activating the aryl hydrocarbon receptor (AHR). However, previous studies showed that individual PAHs may also interact with the constitutive androstane receptor (CAR). Here, we studied ten PAHs, different in carcinogenicity classification, for their potential to activate AHR- and CAR-dependent luciferase reporter genes in human liver cells. The majority of investigated PAHs activated AHR, while non-carcinogenic PAHs tended to activate CAR. We further characterized gene expression, protein abundancies and activities of the AHR targets CYP1A1 and 1A2, and the CAR target CYP2B6 in human HepaRG hepatoma cells. Enzyme induction patterns strongly resembled the profiles obtained at the receptor level, with AHR-activating PAHs inducing CYP1A1/1A2 and CAR-activating PAHs inducing CYP2B6. In summary, this study provides evidence that beside well-known activation of AHR, some PAHs also activate CAR, followed by subsequent expression of respective target genes. Furthermore, we found that an increased PAH ring number is associated with AHR activation as well as the induction of DNA double-strand breaks, whereas smaller PAHs activated CAR but showed no DNA-damaging potential.     

Effect of Grain Size on Mechanical Properties of Submicrometer 3Y-TZP: Fracture Strength and Hydrothermal Degradation

This paper considers fracture strength, fracture origins, and hydrothermal degradation of 3Y-TZP with grain sizes in the range of 110–480 nm. Biaxial fracture strength testing was used to show that the fracture strength increases with grain size and is governed by the concurrent change in fracture toughness. Hydrothermal degradation was studied by means of fractography, Raman microscopy and its effect on fracture strength. Up to 200 nm grain size, hydrothermal degradation of strength is limited. Larger grain sizes exhibit either premature failure or an increase in strength. A surface transformation zone was found to be responsible for both phenomena.     

Reinigung lösungsmittelhaltiger Abluft – alternative Möglichkeiten

Purification of solvents containing air – Alternative methods. Different processes are used for the purification of solvents containing air: condensation, absorption, adsorption, combustion, membrane permeation, and biofilters or bioscrubbers. The processes will be explained by examples. The specifications required by “TA Luft” often cannot be reached only by condensation and membrane permeation. The success of absorption depends on the scrubbing liquid. Glycol ethers are useful scrubbing liquids – especially for chlorinated hydrocarbons. The choice of the process depends on the volume flow rate, the solvent concentration, and the kind of solvent. Recycling of the solvents reduces the costs of the process.     

Detailed Molecular Structure Modeling – A Path Forward to Designing Application Properties of ldPE

Summary: This paper describes a step on the ambitious aim to “design” application properties of ldPE by first simulating the detailed molecular structure of a high‐pressure tubular reactor product. The reactor of a certain configuration produces under well‐defined operating conditions. The next step is to correlate the structure with the application properties. Finally, the sequence will be reversed in order to deduce the operating conditions, which lead to the desired product quality. Two‐dimensional distributions, in molecular weight and branching frequency, as well a two compartment models with a core and a shell stream were simulated and compared with experimental results. Therefore, CFD simulations were carried out to discretize the reaction medium. Samples were taken from both pilot and commercial plants. The TREF‐SEC analytical method was successfully applied in order to measure the microscopic structure of the material. The tremendous numerical problems were solved with the help of the software PREDICI .

Detailed MWD for a pilot scale reactor product.     

Iron(II)‐based catalysts for ethene oligomerization

The synthesis of iron(II) complexes with various tridentate di(imino)pyridine ligands and their potential as ethene oligomerization catalysts are described. The ligands are characterized by ¹H‐ and ¹³C‐NMR spectroscopy and the complexes only by mass spectrometry due to their paramagnetism. After activation either with methylalumoxane (MAO) or with a heterogeneous cocatalyst consisting of partially hydrolyzed trimethylaluminum and silica gel, the prepared complexes proved to be good catalysts for the oligomerization of ethene. 1‐Octene, 1‐hexene, and 1‐decene were the major products, formed in very high isomeric purity (99.9 %). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 476–482, 2003     

Photocrosslinking of stilbene-modified polymers

The reactions of trans-2,5-dimethoxy-4′-aminostilbene with poly(maleic anhydride-co-methylvinyl ether) and trans-2,5-dimethoxy-4′-isocyanatostilbene with poly(oxy-1,4-phenyleneisopropylidene:1,4-phenyleneoxy-2-hydroxytrimethylene) yield polymeric systems which undergo rapid crosslinking upon short exposure to ultraviolet light. The extent of photocrosslinking as a function of exposure time was determined by the decrease of the trans-stilbene ultraviolet absorption at 350 nm.