(11<Emphasis Type="Italic">Z</Emphasis>,13<Emphasis Type="Italic">E</Emphasis>)-Hexadecadien-1-yl Acetate: Sex Pheromone of the Grass Webworm <Emphasis Type="Italic">Herpetogramma licarsisalis</Emphasis>—Identification,Synthesis, and Field Bioassays

The grass webworm Herpetogramma licarsisalis (Lepidoptera: Crambidae), which has recently established in pasture in Northland, New Zealand, is an important pest of many tropical and subtropical grasses. Two pheromone components, (Z)-11-hexadecen-1-yl acetate (Z11–16:Ac) and (11Z,13E)-hexadecadien-1-yl acetate (Z11,E13–16:Ac), were identified in pheromone gland extracts of female moths by gas chromatography (GC), GC-electroantennographic detection, and GC-mass spectrometry in conjunction with microchemical tests (dimethyldisulfide and 4-methyl-1,2,4-triazoline-3,5-dione derivatizations). Z11,E13–16:Ac and its geometric isomer (11E,13Z)-hexadecadien-1-yl acetate (E11,Z13–16:Ac) were synthesized via stereoselective Wittig reactions, and the identity of the diene present in the pheromone glands was confirmed to be Z11,E13–16:Ac. Field bioassays at Indooroopilly in Brisbane, Australia, established that Z11,E13–16:Ac was necessary and sufficient for attraction of male grass webworm moths and that the corresponding alcohol, (11Z,13E)-hexadecadien-1-ol (Z11,E13–16:OH), had a strong inhibitory effect on trap catches at the ratios tested. When mixed with Z11,E13–16:Ac in various ratios, Z11–16:Ac had no effect on the attractiveness of lures. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The cyclotide fingerprint in oldenlandia affinis: elucidation of chemically modified, linear and novel macrocyclic peptides

The complete suite of cyclotides present in Oldenlandia affinis (Rubiaceae), the plant that was originally found to contain this unique family of circular proteins, has been characterised. This study expands the number of known cyclotides in this plant to 17, of which nine new sequences (kalata B9-B17) were characterised in this work. In addition, five derivatives that contain oxidation products of the conserved tryptophan were identified, and it was shown that the formation of these derivatives is catalysed by exposure to sunlight. Furthermore, we describe two "linear" cyclotide analogues. These acyclic peptides have three intact disulfide bonds, and their N and C termini coincide with the hypothesised cleavage sites from the precursor protein. This work increases our knowledge about the sequence variation that is accommodated by the cyclic cystine knot scaffold, confirms its applicability as a template for drug design, and also shows the first natural degradation pathways for cyclotides. These pathways have important implications for the persistence and environmental fate of the cyclotides if used as crop-protection agents.     

Chromogenic assay for phospholipase D from Streptomyces chromofuscus: Application to the evaluation of substrate analogs

A rapid and convenient chromogenic assay for phospholipase D from Streptomyces chromofuscus (PLD_Sc) has been developed that converts the choline generated from the enzyme-catalyzed hydrolysis of phospholipids into a chromogenic dye. By quenching the reaction with EDTA at defined times, an initial rate curve is produced from which a k _cat and K _m can be readily derived. This assay has been applied to the biological evaluation of several substrate analogs, all of which appear to be activators rather than substrates or inhibitors of this enzyme. Performing the assay in 96-well microtiter plates allows for the easy screening of potential effectors of this enzyme.     

UVB Radiation Variably Affects n-3 Fatty Acids but Elevated Temperature Reduces n-3 Fatty Acids in Juvenile Atlantic Salmon (Salmo salar)

Temperature and ultraviolet B radiation (UVB 290–320?nm) are inextricably linked to global climate change. These two variables may act separately, additively, or synergistically on specific aspects of fish biochemistry. We raised Atlantic Salmon (Salmo salar) parr for 54?days in outdoor tanks held at 12 and 19?°C and, at each temperature, we exposed them to three spectral treatments differing in UV radiation intensity. We quantified individual fatty acid (FA) mass fractions in four tissues (dorsal muscle, dorsal and ventral skin, and ocular tissue) at each temperature?×?UV combination. FA composition of dorsal muscle and dorsal and ventral skin was not affected by UV exposure. Mass fractions of 16:0, 18:0, and saturated fatty acids (SFA) were greater in dorsal muscle of warm-reared fish whereas 18:3n-3, 20:2, 20:4n-6, 22:5n-3, 22:6n-3, n-3, n-6, polyunsaturated fatty acids (PUFA), and total FA were significantly higher in cold-reared fish. Mass fractions of most of the FA were greater in the dorsal and ventral skin of warm-reared fish. Cold-reared salmon exposed to enhanced UVB had higher ocular tissue mass fractions of 20:2, 20:4n-6, 22:6n-3, n-3, n-6, and PUFA compared to fish in which UV had been removed. These observations forecast a host of ensuing physiological and ecological responses of juvenile Atlantic Salmon to increasing temperatures and UVB levels in native streams and rivers where they mature before smolting and returning to the sea.     

Synthesis and Photocatalytic Properties of Single Crystalline (Ga1-xZnx)(N1-xOx) Nanotubes

Recently, (Ga_1-xZn_x)(N_1-xO_x) has gained widespread attention as a comparatively high efficiency photocatalyst for visible-light-driven overall water splitting. Despite significant gains in efficiency over the past several years, a majority of the photogenerated carriers recombine within bulk powders. To improve the photocatalytic activity, we used an epitaxial casting method to synthesize single-crystalline, high surface area (Ga_1-xZn_x)(N_1-xO_x) nanotubes with ZnO compositions up to x=0.10. Individual nanotubes showed improved homogeneity over powder samples due to a well defined epitaxial interface for ZnO diffusion into GaN. Absorption measurements showed that the ZnO incorporation shifts the absorption into the visible region with a tail out to 500 nm. Gas chromatography (GC) was used to compare the solar water splitting activity of (Ga_1-xZn_x)(N_1-xO_x) nanotubes (x=0.05–0.10) with similar composition powders. Cocatalyst decorated samples were dispersed in aqueous solutions of CH₃OH and AgO₂CCH₃ to monitor the H⁺ reduction and H₂O oxidation half reactions, respectively. The nanotubes were found to have approximately 1.5–2 times higher photocatalytic activity than similar composition powders for the rate limiting H⁺ reduction half reaction. These results demonstrate that improvements in homogeneity and surface area using the nanotube geometry can enhance the photocatalytic activity of GaN:ZnO for solar water splitting.     

Multiple Chemical Features Impact Biological Performance Diversity of a Highly Active Natural Product-Inspired Library

A systematic, diversity-oriented synthesis approach was employed to access a natural product-inspired flavonoid library with diverse chemical features, including chemical properties, scaffold, stereochemistry, and appendages. Using Cell Painting, the effects of these diversity elements were evaluated, and multiple chemical features that predict biological performance diversity were identified. Scaffold identity appears to be the dominant predictor of performance diversity, but stereochemistry and appendages also contribute to a lesser degree. In addition, the diversity of chemical properties contributed to performance diversity, and the driving chemical property was dependent on the scaffold. These results highlight the importance of key chemical features that may inform the creation of small-molecule, performance-diverse libraries to improve the efficiency and success of high-throughput screening campaigns.     

Preparation,thermal and mechanical properties of poly (ether-imide) composite reinforced with carbon nanotube buckypaper

Vacuum filtration technique was employed in order to prepare multiwalled carbon nanotube buckypapers (MWCNT-BP) through a well-dispersed suspension of MWCNT/H₂O with the aid of Triton X-100 surfactant. The obtained BP (buckypaper) was then infiltrated with a solution of poly (ether-imide) (PEI) under vacuum conditions. The visual inspection demonstrated the importance of the centrifugation procedure before the vacuum filtration of the suspension, revealing a smooth surface of the as-prepared buckypaper. Thermogravimetric experiments (TGA) and scanning electron microscopy analyses have demonstrated the role of isopropyl alcohol in the removal of Triton X-100 from the nanotube network. SEM observations of the cross-section view of the samples revealed a porous network of the fabricated BP, and an impregnated structure of the PEI/BP composite, suggesting a good interfacial bonding between MWCNT and PEI. Moreover, significant improvements were achieved in mechanical and thermal properties of PEI matrix by the incorporation of BP, as the increase of both the storage modulus (42%) and the T _g (11 °C) for the PEI/BP composite. TGA have shown a significant increase in the onset decomposition temperature of the polymer by the incorporation of the BP. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48330.     

Glutathione-S-transferase M1 regulation of diesel exhaust particle-induced pro-inflammatory mediator expression in normal human bronchial epithelial cells

ABSTRACT: BACKGROUND: Diesel exhaust particles (DEP) contribute substantially to ambient particulate matter (PM) air pollution in urban areas. Inhalation of PM has been associated with increased incidence of lung disease in susceptible populations. We have demonstrated that the glutathione Stransferase M1 (GSTM1) null genotype could aggravate DEP-induced airway inflammation in human subjects. Given the critical role airway epithelial cells play in the pathogenesis of airway inflammation, we established the GSTM1 deficiency condition in primary bronchial epithelial cells from human volunteers with GSTM1 sufficient genotype (GSTM1+) using GSTM1 shRNA to determine whether GSTM1 deficiency could exaggerate DEP-induced expression of interleukin-8 (IL-8) and IL-1beta proteins. Furthermore, the mechanisms underlying GSTM1 regulation of DEP-induced IL-8 and IL-1beta expression were also investigated. METHODS: IL-8 and IL-1beta protein levels were measured using enzyme-linked immunosorbent assay. GSTM1 deficiency in primary human bronchial epithelial cells was achieved using lentiviral GSTM1 shRNA particles and verified using real-time polymerase chain reaction and immunoblotting. Intracellular reactive oxygen species (ROS) production was evaluated using flow cytometry. Phosphorylation of protein kinases was detected using immunoblotting. RESULTS: Exposure of primary human bronchial epithelial cells (GSTM1+) to 25-100 mug/ml DEP for 24 h significantly increased IL-8 and IL-1beta protein expression. Knockdown of GSTM1 in these cells further elevated DEP-induced IL-8 and IL-1beta expression, implying that GSTM1 deficiency aggravated DEP-induced pro-inflammatory response. DEP stimulation induced the phosphorylation of extracellular signal-regulated kinase (ERK) and Akt, the downstream kinase of phosphoinositide 3-kinase (PI3K), in GSTM1+ bronchial epithelial cells. Pharmacological inhibition of ERK kinase and PI3K activity blocked DEP-induced IL-8 and IL-1beta expression. DEP-induced ERK and Akt phosphorylation could be increased by GSTM1 knockdown. In addition, pretreatment of HBEC with the antioxidant N-acetyl cysteine significantly inhibited DEP-induced ERK and Akt phosphorylation, and subsequent IL-8 and IL-beta expression. CONCLUSION: GSTM1 regulates DEP-induced IL-8 and IL-1beta expression in primary human bronchial epithelial cells by modulation of ROS, ERK and Akt signaling.     

Extracellular Vesicles: Messengers of p53 in Tumor–Stroma Communication and Cancer Metastasis

Tumor progression to a metastatic and ultimately lethal stage relies on a tumor-supporting microenvironment that is generated by reciprocal communication between tumor and stromal host cells. The tumor–stroma crosstalk is instructed by the genetic alterations of the tumor cells—the most frequent being mutations in the gene Tumor protein p53 (TP53) that are clinically correlated with metastasis, drug resistance and poor patient survival. The crucial mediators of tumor–stroma communication are tumor-derived extracellular vesicles (EVs), in particular exosomes, which operate both locally within the primary tumor and in distant organs, at pre-metastatic niches as the future sites of metastasis. Here, we review how wild-type and mutant p53 proteins control the secretion, size, and especially the RNA and protein cargo of tumor-derived EVs. We highlight how EVs extend the cell-autonomous tumor suppressive activity of wild-type p53 into the tumor microenvironment (TME), and how mutant p53 proteins switch EVs into oncogenic messengers that reprogram tumor–host communication within the entire organism so as to promote metastatic tumor cell dissemination.