The molecular structure of asphaltene: an unfolding story

From detailed chemical and thermal degradation studies, a host of structural units have been identified in Alberta asphaltenes. It has been shown that the extent of aromatic condensation is low and that highly condensed pericyclic aromatic structures are present in very low concentrations. From the available data reported to date, it is concluded that petroleum asphaltenes were mainly derived through the catalytic cyclization, aromatization and condensation of n-alkanoic, probably fatty acids, precursors.     

An experimental study of plasticating in a reciprocating-screw injection molding machine

Experimental studies were performed with low density polyethylene, acrylonitrile-butadiene-styrene polymers and on polyvinyl chloride to elucidate the nature of the plasticating process in a reciprocating-screw injection molding machine. Melting data, obtained by use of the “cooling experiment,” and plastic temperature data reveal that the screw recharge process is a transient plasticating extrusion process which gradually approaches the equilibrium extrusion behavior as the screw rotates. If the screw rotation time is a high percentage of the total cycle time, the plasticating behavior is very similar to steady-state extrusion behavior, but if the screw rotation time is a small percentage of the total cycle time, the plasticating behavior is significantly different. Furthermore, better plasticating is obtained by use of a low RPM and high percentage rotation time than by a high RPM and low percentage rotation time.     

Defensive secretion of the carabid beetlePasimachus subsulcatus

The defensive secretion of the carabid beetlePasimachus subsulcatus is a concentrated solution (up to 90%) of carboxylic acids, amounting to about 1% of body mass. It contains three major components (methacrylic, tiglic, and angelic acids) and four minor components (isobutyric, 2-methyl-butyric, isovaleric, and senecioic acids). In the single population of this large flightless beetle that was examined, the relative ratio of acidic components was remarkably constant from individual to individual.Report No. 87 of the series Defense Mechanisms of Arthropods; No. 86 is Dussourd, D., et al.,Proc. Natl. Acad. Sci. 85, 5992 (1988).     

Rubber elasticity of poly(n-butyl acrylate) networks formed with multifunctional crosslinkers

The rubber elasticity characteristics of poly(n-butyl acrylate) networks crosslinked with tetrafunctional (EGDM and TEGDM), hexafunctional (TMPTM), and octafunctional (PETMA) vinyl crosslinkers were investigated. Both gel—sol analyses and crosslinking efficiency theories were used to evaluate the chemical crosslink contribution v_c and the entanglement contribution v_p to the elastically effective network chains v_e, and the effect of the crosslink junction functionality f on the front factor g. The front factors obtained were in the range of 0.50–0.92, depending upon the network system and the counting method for v_c. The relationship of g = [(f ? 2)/f]/〈r²〉/〈r²〉_o seems reasonable in the case of the tetrafunctional and hexafunctional networks, but deviates in the case of the octafunctional network. It is also evident that the functionality scheme for the front factor could only be valid under the postulate of a high v_p, which increases with increasing v_c, especially in the high v_c region near the Gaussian limit. The average energetic contribution to the retractive force of the present systems, expressed as F_e/F, is ?0.30 ± 0.1.     

Transformation Toughening in Large-Grain-Size CeO2-Doped ZrO2 Polycrystals

The fracture and transformation behavior of tetragonal polycrystalline ZrO₂ alloys containing 18 mol% CeO₂ (Ce-TZP) was investigated. In the absence of applied stress the tetragonal phase was found to be stable in large-grained (>30 μm) samples at room temperature. The monoclinic phase was detected in regions of high residual stress near hardness indentations although no evidence of a wake of monoclinic phase along the fracture surface was observed. The fracture toughness increased from 4 to 7 MPa · m^1/2 as density and/or grain size increased. It is proposed that the relatively high toughness of these materials is due to the occurrence of stress-driven tetragonal-to-monoclinic transformation near the crack tip, which reverses when the crack has passed.     

Investigation of the Antiproliferative Properties of Natural Sesquiterpenes from Artemisia asiatica and Onopordum acanthium on HL-60 Cells in Vitro

Plants and plant extracts play a crucial role in the research into novel antineoplastic agents. Four sesquiterpene lactones, artecanin (1), 3β-chloro-4α,10α-dihydroxy-1α,2α-epoxy-5α,7αH-guaia-11(13)-en-12,6α-olide (2), iso-seco-tanapartholide 3-O-methyl ether (3) and 4β,15-dihydro-3-dehydrozaluzanin C (4), were isolated from two traditionally used Asteraceae species (Onopordum acanthium and Artemisia asiatica). When tested for antiproliferative action on HL-60 leukemia cells, these compounds exhibited reasonable IC₅₀ values in the range 3.6–13.5 μM. Treatment with the tested compounds resulted in a cell cycle disturbance characterized by increases in the G1 and G2/M populations, while there was a decrease in the S phase. Additionally, 1–3 elicited increases in the hypodiploid (subG1) population. The compounds elicited concentration-dependent chromatin condensation and disruption of the membrane integrity, as revealed by Hoechst 33258–propidium staining. Treatment for 24 h resulted in significant increases in activity of caspases-3 and -9, indicating that the tested sesquiterpenes induced the mitochondrial pathway of apoptosis. The proapoptotic properties of the sesquiterpene lactones were additionally demonstrated withannexin V staining. Compounds 1 and 2 increased the Bax/Bcl-2 expression and decreased the expressions of CDK1 and cyclin B2, as determined at the mRNA level by means of RT-PCR. These experimental results indicate that sesquiterpene lactones may be regarded as potential starting structures for the development of novel anticancer agents.     

A Catalyst‐Directed Remote Stereogenic Center Switch During the Site‐Selective Aldol Desymmetrization of Cyclohexanone‐Based Diketones

Site‐selectivity, differentiating members of the same functional group type on one substrate, is an emerging tactic for shortened advanced building block and biomolecule synthesis. Despite its potential, site‐selectivity remains less studied and especially so for ketone‐based substrates. During this work ketone site‐selectivity has been coupled with the chiral amine‐catalyzed aldol desymmetrization of 4‐keto‐substituted cyclohexanones, allowing three stereogenic centers to form in the aldol product while leaving the acyclic ketone unreacted. Unique here, compared to all previous 4‐substituted cyclohexanone desymmetrizations, is the first access to synthetically useful quantities of an epimeric (remote stereogenic center) aldol product. To demonstrate the value of these aldol products, we show their elaboration into eight keto‐acetonide and one keto‐lactone products. All compounds were isolated as single diastereomers and in high ee (≥96%). These efforts represent the first full characterization of aldol products with type III, Figure 2, relative stereochemistry, regardless of the enantiomer formed.

     

Effect of Methionine Sulfoxide on the Synthesis and Purification of Aggregation-Prone Peptides

A two-step synthesis for methionine-containing hydrophobic and/or aggregation-prone peptides is presented that takes advantage of the reversibility of methionine oxidation. The use of polar methionine sulfoxide as a building block in solid-phase peptide synthesis improves the synthesis quality and yields the crude peptide, with significantly improved solubility compared to the reduced species. This facilitates the otherwise often laborious peptide purification by high-performance liquid chromatography. The subsequent reduction proceeds quantitatively. This approach has been optimised with the methionine-rich Tar-DNA-binding protein 43 (307–347), but is also more generally applicable, as demonstrated by the syntheses of human calcitonin and two aggregation-prone peptides from the human prion protein.