The Effect of Age and Intrinsic Aerobic Exercise Capacity on the Expression of Inflammation and Remodeling Markers in Rat Achilles Tendons

Old age, adiposity, and metabolic disorders are known as risk factors for chronic tendinopathy, which is a common problem in both athletes and the general population. However, the importance of these influencing factors has not yet been well understood. This study investigated alterations in gene expression and histology of Achilles tendons of young (10 weeks) and old (100 weeks) rats bred for low (low capacity runners, LCR) and high (high capacity runners, HCR) intrinsic aerobic exercise capacity. In this rat model, LCR displayed a phenotype of reduced exercise capacity, higher body weight, and metabolic dysfunctions compared to HCR. We hypothesized that the risk factors for tendinopathy in old LCR could lead to more pronounced impairments in Achilles tendon tissue. In quantitative real-time PCR (qPCR), age-related downregulation of tenocyte markers e.g., tenomodulin, genes related to matrix modeling and remodeling (e.g., collagens, elastin, biglycan, fibronectin, tenascin C) as well as transforming growth factor beta 3 (Tgfb3) have been detected. Inflammation marker cyclooxygenase 2 (Cox2) was downregulated in old rats, while microsomal prostaglandin E synthase 2 (Ptges2) was upregulated in old HCR and old LCR. In all groups, interleukin 6 (Il6), interleukin 1 beta (Il1b), and tumor necrosis factor alpha (Tnfa) showed no significant alteration. In histological evaluation, tendons of old rats had fewer and more elongated tenocyte nuclei than young rats. Even though a higher content of glycosaminoglycans, a sign of degeneration, was found in old HCR and LCR, no further signs of tendinopathy were detectable in tendons of old rats by histological evaluation. Low intrinsic aerobic exercise capacity and the associated phenotype did not show significant effects on gene expression and tendon histology. These findings indicate that aging seems to play a prominent role in molecular and structural alterations of Achilles tendon tissue and suggests that other risk factors associated with intrinsic aerobic exercise capacity are less influential in this rat model.     

Sex Attractant Pheromone of the Luna Moth, <Emphasis Type="Italic">Actias luna</Emphasis> (Linnaeus)

Giant silk moths (Lepidoptera: Saturniidae) typically are not well represented as larvae or adults in community level inventories of Lepidoptera, and as a result, little is known about their population dynamics. Furthermore, in recent years, many species of silk moths appear to have experienced population declines. Volatile sex pheromones are powerful sampling tools that can be used in operational conservation and monitoring programs for insects. Here, we describe the identification of the sex attractant pheromone of a giant silk moth, the luna moth Actias luna. Coupled gas chromatography-electroantennographic detection and gas chromatography-mass spectrometric analyses of extracts from pheromone glands of female luna moths supported the identification of (6E,11Z)-6,11-octadecadienal (E6,Z11–18:Ald), (6E)-6-octadecenal (E6–18:Ald), and (11Z)-11-octadecenal (Z11–18:Ald) as the compounds in extracts that elicited responses from antennae of male moths. These identifications were confirmed by synthesis, followed by testing of blends of the synthetic compounds in field trials in Ontario, Canada, and Kentucky, USA. Male moths were attracted to synthetic E6,Z11–18:Ald as a single component. Attraction appeared to be enhanced by addition of E6–18:Ald but not Z11–18:Ald, suggesting that the luna moth pheromone consists of a blend of E6,Z11–18:Ald and E6–18:Ald.     

The Role of a Nonribosomal Peptide Synthetase in l‐Lysine Lactamization During Capuramycin Biosynthesis

Capuramycins are one of several known classes of natural products that contain an l ‐Lys‐derived l ‐α‐amino‐?‐caprolactam (l ‐ACL) unit. The α‐amino group of l ‐ACL in a capuramycin is linked to an unsaturated hexuronic acid component through an amide bond that was previously shown to originate by an ATP‐independent enzymatic route. With the aid of a combined in vivo and in vitro approach, a predicted tridomain nonribosomal peptide synthetase CapU is functionally characterized here as the ATP‐dependent amide‐bond‐forming catalyst responsible for the biosynthesis of the remaining amide bond present in l ‐ACL. The results are consistent with the adenylation domain of CapU as the essential catalytic component for l ‐Lys activation and thioesterification of the adjacent thiolation domain. However, in contrast to expectations, lactamization does not require any additional domains or proteins and is likely a nonenzymatic event. The results set the stage for examining whether a similar NRPS‐mediated mechanism is employed in the biosynthesis of other l ‐ACL‐containing natural products and, just as intriguingly, how spontaneous lactamization is avoided in the numerous NRPS‐derived peptides that contain an unmodified l ‐Lys residue.     

High-entropy boride–carbide ceramics by sequential boro/carbothermal synthesis

A dual-phase high-entropy boride (HEB)/carbide (HEC) ceramic with a fine grain size was synthesized by a sequential boro/carbothermal process. In the first step, an Hf–Nb–Ta–Ti–Zr-containing carbide was synthesized by a carbothermal reduction of oxides followed by the reaction of the carbide with B₄C and ZrH₂ to convert part of the carbide to boride. The resulting composition was ∼29 vol% HEB with an average grain size of ∼1.1 μm. Solid solution formation occurred at the densification temperature of 1900°C resulting in a relative density higher than 99%. The Vickers hardness was 26.5 ± 1.4 GPa. This is the first report of synthesizing dual-phase boride–carbide high-entropy ceramics from carbothermally synthesized, HEC powders.     

Glass Dielectrics in Extreme High‐Temperature Environment

Thin and flexible glass ribbons can be rolled into a film capacitor structures for power electronic circuits. Glass has excellent electrical properties and is a leading candidate to replace polymer films for high‐temperature applications. The dielectric properties of a low‐alkali aluminoborosilicate glass were characterized up to temperatures of 400°C. Low‐field permittivity values of 6 with dielectric loss below 0.01 were found for temperatures below 300°C. The dielectric breakdown strength exceeded 5 MV/cm for temperature of 400°C and high‐field polarization measurements showed that glass has over 95% energy efficiency at temperatures of 200°C, which is a target temperature for high‐temperature power electronic circuits driven by wide bandgap semiconductor devices.     

Gold(I)‐Catalysed Cyclisation of Alkynoic Acids: Towards an Efficient and Eco‐Friendly Synthesis of γ‐, δ‐ and ϵ‐Lactones

The improved synthesis of γ‐, δ‐ and ϵ‐lactones using a dinuclear N‐heterocyclic carbene (NHC)‐gold(I) catalyst is reported. This solvent‐free process provides access to γ‐ and δ‐lactones in high regio‐ and stereoselectivity. Reactions were performed at low catalyst loadings and without the need for any additives. The use of a digold pre‐catalyst provides a new synthetic route to functionalised ϵ‐lactones, poorly accessible using previous methodologies.

     

Identification of Components of the Aggregation Pheromone of the Guam Strain of Coconut Rhinoceros Beetle,Oryctes rhinoceros,and Determination of Stereochemistry

The coconut rhinoceros beetle, Oryctes rhinoceros (Linnaeus 1758) (Coleoptera: Scarabaeidae: Dynastinae) (CRB), is endemic to tropical Asia where it damages both coconut and oil palm. A new invasion by CRB occurred on Guam in 2007 and eradication attempts failed using commonly applied Oryctes rhinoceros nudivirus (OrNV) isolates. This and subsequent invasive outbreaks were found to have been caused by a previously unrecognized haplotype, CRB-G, which appeared to be tolerant to OrNV. The male-produced aggregation pheromone of the endemic, susceptible strain of O. rhinoceros (CRB-S) was previously identified as ethyl 4-methyloctanoate. Following reports from growers that commercial lures containing this compound were not attractive to CRB-G, the aim of this work was to identify the pheromone of CRB-G. Initial collections of volatiles from virgin male and female CRB-G adults from the Solomon Islands failed to show any male- or female-specific compounds as candidate pheromone components. Only after five months were significant quantities of ethyl 4-methyloctanoate and 4-methyloctanoic acid produced by males but not by females. No other male-specific compounds could be detected, in particular methyl 4-methyloctanoate, 4-methyl-1-octanol, or 4-methyl-1-octyl acetate, compounds identified in volatiles from some other species of Oryctes. Ethyl 4-methyloctanoate elicited a strong electroantennogram response from both male and female CRB-G, but these other compounds, including 4-methyloctanoic acid, did not. The enantiomers of ethyl 4-methyloctanoate and 4-methyloctanoic acid were conveniently prepared by enzymatic resolution of the commercially-available acid, and the enantiomers of the acid, but not the ester, could be separated by gas chromatography on an enantioselective cyclodextrin phase. Using this approach, both ethyl 4-methyloctanoate and 4-methyloctanoic acid produced by male CRB-G were shown to be exclusively the (R)-enantiomers whereas previous reports had suggested male O. rhinoceros produced the (S)-enantiomers. However, re-examination of the ester and acid produced by male CRB-S from Papua New Guinea showed that these were also the (R)-enantiomers. In field trapping experiments carried out in the Solomon Islands, both racemic and ethyl (R)-4-methyloctanoate were highly attractive to both male and female CRB-G beetles. The (S)-enantiomer and the corresponding acids were only weakly attractive. The addition of racemic 4-methyloctanoic acid to ethyl 4-methyloctanoate did significantly increase attractiveness, but the addition of (R)- or (S)-4-methyloctanoic acid to the corresponding ethyl esters did not. Possible reasons for the difference in assignment of configuration of the components of the CRB pheromone are discussed along with the practical implications of these results.

     

Asymmetric synthesis and conformational analysis by NMR spectroscopy and MD of Aba- and α-MeAba-containing dermorphin analogues

Dermorphin analogues, containing a (S)‐ and (R)‐4‐amino‐1,2,4,5‐tetrahydro‐2‐benzazepin‐3‐one scaffold (Aba) and the α‐methylated analogues as conformationally constrained phenylalanines, were prepared. Asymmetric phase‐transfer catalysis was unable to provide the (S)‐α‐Me‐o‐cyanophenylalanine precursor for (S)‐α‐MeAba in acceptable enantiomeric purity. However, by using a Schöllkopf chiral auxiliary, this intermediate was obtained in 88 % ee. [(S)‐Aba 3‐Gly 4]dermorphin retained μ‐opioid affinity but displayed an increased δ‐affinity. The corresponding R epimer was considerably less potent. In contrast, the [(R)‐α‐MeAba 3‐Gly 4]dermorphin isomer was more potent than its S epimer. Tar‐MD simulations of both non‐methylated [Aba 3‐Gly 4]dermorphin analogues showed a degree of folding at the C‐terminal residues toward the N terminus of the peptide, without however, adopting a stabilized β‐turn conformation. The α‐methylated analogues, on the other hand, exhibited a type I/I′ β‐turn conformation over the α‐MeAba 3 and Gly 4 residues, which was stabilized by a hydrogen bond involving Tyr 5‐H_N and D ‐Ala 2‐CO.     

INTERFACE/INTERPHASE ENGINEERING OF POLYMERS FOR ADHESION ENHANCEMENT: PART II. THEORETICAL AND TECHNOLOGICAL ASPECTS OF SURFACE-ENGINEERED INTERPHASE-INTERFACE SYSTEMS FOR ADHESION ENHANCEMENT

Part I of this paper reviewed the theoretical principles of the macromolecular design of polymer interface/interphase systems for obtaining maximum adhesion and fracture performance of adhesively bonded assemblies. In Part II a novel, relatively simple and industry-feasible technology for surface-grafting connector molecules is demonstrated and discussed in detail and supported by a range of experimental examples. It is shown, in agreement with contemporary theory, that the use of chemically attached graft chemicals of controlled spatial geometry and chemical functionality enables a significant increase in the strength and fracture energy of the interphase, to the point of cohesive fracture of the substrate, or that of an adjacent medium such as adhesive, elastomer, or other material. This occurs even after prolonged exposure of investigated systems to adverse environments such as hot water.     

Vitreous carbon micro-lattice structures

A new approach is presented to fabricate open-cellular carbon materials with an ordered, lattice-type micro-scale architecture. The carbon micro-lattice materials were fabricated by pyrolyzing a polymer precursor template formed from an interconnected three-dimensional array of self-propagating photopolymer waveguides. Impregnating the polymer precursor template with acrylonitrile increased the carbon yield of the material from 19% to 46%. Structural analysis and density measurements of the solid carbon phase are consistent with vitreous carbon. Compression experiments yielded a compressive modulus (E) of 1.1 GPa and a failure strength (σ_f) of 10.2 MPa for a structure with relative density of 12.8%.