Multifunctionalised benzoxazinones in the systems Oryza sativa–Echinochloa crus‐galli and Triticum aestivum–Avena fatua as natural‐product‐based herbicide leads

BACKGROUND: Fifteen novel derivatives of D‐DIBOA, including aromatic ring modifications and the addition of side chains in positions C‐2 and N‐4, had previously been synthesised and their phytotoxicity on standard target species (STS) evaluated. This strategy combined steric, electronic, solubility and lipophilicity requirements to achieve the maximum phytotoxic activity. An evaluation of the bioactivity of these compounds on the systems Oryza sativa–Echinochloa crus‐galli and Triticum aestivum–Avena fatua is reported here. RESULTS: All compounds showed inhibition profiles on the two species Echinochloa crus‐galli (L.) Beauv. and Avena fatua L. The most marked effects were caused by 6F‐4Pr‐D‐DIBOA, 6F‐4Val‐D‐DIBOA, 6Cl‐4Pr‐D‐DIBOA and 6Cl‐4Val‐D‐DIBOA. The IC₅₀ values for the systems Echinochloa crus‐galli–Oryza sativa and Avena fatua–Triticum aestivum for all compounds were compared. The compound that showed the greatest selectivity for the system Echinochloa crus‐galli–Oryza sativa was 8Cl‐4Pr‐D‐DIBOA, which was 15 times more selective than the commercial herbicide propanil (Cotanil‐35). With regard to the system Avena fatua–Triticum aestivum, the compounds that showed the highest selectivities were 8Cl‐4Val‐D‐DIBOA and 6F‐4Pr‐D‐DIBOA. The results obtained for 6F‐4Pr‐D‐DIBOA are of great interest because of the high phytotoxicity to Avena fatua (IC₅₀ = 6 µM , r² = 0.9616). CONCLUSION: The in vitro phytotoxicity profiles and selectivities shown by the compounds described here make them candidates for higher‐level studies. 8Cl‐4Pr‐D‐DIBOA for the system Echinochloa crus‐galli‐Oryza sativa and 6F‐4Pr‐D‐DIBOA for Avena fatua‐Triticum aestivum were the most interesting compounds. Copyright © 2010 Society of Chemical Industry     

Primary and secondary metabolite composition of kernels from three cultivars of Portuguese chestnut (Castanea sativa Mill.) at different stages of industrial transformation

Chestnut (Castanea sativa) is an important basic food in rural diets and a major starch crop used in a similar way to potatoes. Chestnuts are a fundamental economic resource in the "chestnut regions" not only for the fruit but also for the chestnut wood. Chestnuts have become increasingly important with respect to human health, for example, as an alternative gluten-free flour source. Chestnuts are also a rich source of other beneficial compounds, but there have been few studies on the composition during processing. In this study, we analyzed the chemical composition of three Portuguese cultivars at different stages of industrial processing. The chestnut cultivars were Longal, Judia, and Martaínha. All three cultivars had high moisture contents but were low in ash, crude fat, and crude protein contents, with high starch and low fiber contents. The free amino acid contents, including various essential amino acids, varied depending on the cultivar. All three cultivars also had a significant content of polyphenolics with gallic acid; ellagic acid was predominant among hydrolyzable and condensed tannins. Many of these compounds are known to exert significant positive effects on human health. The one-way analysis of variance for fresh chestnut shows significant differences among the three cultivars for most of the studied parameters. The same statistical analysis applied to each one of the two cultivars (Judia and Longal) sampled for the four processing steps analyzed indicates a significant effect of this factor in practically all of the constituents. On the other hand, the two-way analysis of variance shows that, besides the residual, the processing step and the interaction cultivar x processing step were the factors that more contributed for the total variation observed in the constituents analyzed, while the contribution of cultivar was much less significant.     

Effect of germination on the carbohydrate composition of the dietary fiber of peas (Pisum sativum L.)

The effect of different conditions of pea germination on dietary fiber (DF) composition was studied. Insoluble dietary fiber (IDF) and soluble dietary fiber (SDF) were subjected to acid hydrolysis, and the resultant neutral sugars, uronic acids, and Klason lignin were quantified. Germinated peas exhibited significantly higher contents of total dietary fiber (TDF) than the raw sample, due to the increases of both DF fractions. Under darkness conditions, germination exhibited the highest contents of IDF and SDF. Decreasing IDF/SDF ratios showed that the carbohydrate changes did not take place to the same extent during germination, the SDF fraction being the most affected. The detailed chemical composition of fiber fractions reveals increases of cellulose in the IDF of germinated samples, whereas SDF exhibits a decrease of pectic polysaccharides and also increases of polysaccharides rich in glucose and mannose. The DF results were corroborated by a comparative examination of the cell wall carbohydrate composition.     

Free amino acid composition of quince (Cydonia oblonga Miller) fruit (pulp and peel) and jam

Twenty-one free amino acids present in several samples of quince fruit (pulp and peel) and quince jam (homemade and industrially manufactured) were analyzed by GC/FID. The analyses showed some differences between quince pulps and peels. Generally, the highest content in total free amino acids and in glycine was found in peels. As a general rule, the three major free amino acids detected in pulps were aspartic acid, asparagine, and hydroxyproline. For quince peels, usually, the three most abundant amino acids were glycine, aspartic acid, and asparagine. Similarly, for quince jams the most important free amino acids were aspartic acid, asparagine, and glycine or hydroxyproline. This study suggests that the free amino acid analysis can be useful for the evaluation of quince jam authenticity. It seems that glycine percentage can be used for the detection of quince peel addition while high alanine content can be related to pear addition.     

Permeability profile estimation of flavonoids and other phenolic compounds by biopartitioning micellar capillary chromatography

This paper points out the usefulness of biopartitioning micellar chromatography (BMC) using capillary columns as a high-throughput primary screening tool providing key information about the oral absorption, skin permeability, and brain-blood distribution coefficients of 15 polyphenols (6 flavones, 2 flavonols, a flavanone, 2 flavan-3-ols, 3 phenolic acids, and a phloroglucinol) in a simple and economical way. For the compounds studied, except vicenin-2, rutin, chlorogenic acid, p-hydroxycinnamic acid, and 4-hydroxybenzoic acid, maximal oral absorption (>90%) can be expected, if there are not solubility problems or metabolic processes. On the other hand, the most retained compounds in BMC, that is, 5-hydroxyflavone, flavone, and flavanone, show the highest brain-blood distribution coefficients and skin permeability coefficients.     

Lithothamnion muelleri Controls Inflammatory Responses,Target Organ Injury and Lethality Associated with Graft-versus-Host Disease in Mice

Lithothamnion muelleri (Hapalidiaceae) is a marine red alga, which is a member of a group of algae with anti-inflammatory, antitumor, and immunomodulatory properties. The present study evaluated the effects of treatment with Lithothamnion muelleri extract (LM) in a model of acute graft-versus-host disease (GVHD), using a model of adoptive splenocyte transfer from C57BL/6 donors into B6D2F1 recipient mice. Mice treated with LM showed reduced clinical signs of disease and mortality when compared with untreated mice. LM-treated mice had reduced tissue injury, less bacterial translocation, and decreased levels of proinflammatory cytokines and chemokines (interferon-γ (IFN-γ), tumor necrosis factor-α (TNF-α), chemokine (C-C motif) ligand 2 (CCL2), chemokine (C-C motif) ligand 3 (CCL3) and chemokine (C-C motif) ligand 5 (CCL5)). The polysaccharide-rich fraction derived from LM could inhibit leukocyte rolling and adhesion in intestinal venules, as assessed by intravital microscopy. LM treatment did not impair the beneficial effects of graft-versus-leukaemia (GVL). Altogether, our studies suggest that treatment with Lithothamnion muelleri has a potential therapeutic application in GVHD treatment.     

Anti HSV-1 Activity of Halistanol Sulfate and Halistanol Sulfate C Isolated from Brazilian Marine Sponge Petromica citrina (Demospongiae)

The n-butanol fraction (BF) obtained from the crude extract of the marine sponge Petromica citrina, the halistanol-enriched fraction (TSH fraction), and the isolated compounds halistanol sulfate (1) and halistanol sulfate C (2), were evaluated for their inhibitory effects on the replication of the Herpes Simplex Virus type 1 (HSV-1, KOS strain) by the viral plaque number reduction assay. The TSH fraction was the most effective against HSV-1 replication (SI = 15.33), whereas compounds 1 (SI = 2.46) and 2 (SI = 1.95) were less active. The most active fraction and these compounds were also assayed to determine the viral multiplication step(s) upon which they act as well as their potential synergistic effects. The anti-HSV-1 activity detected was mediated by the inhibition of virus attachment and by the penetration into Vero cells, the virucidal effect on virus particles, and by the impairment in levels of ICP27 and gD proteins of HSV-1. In summary, these results suggest that the anti-HSV-1 activity of TSH fraction detected is possibly related to the synergic effects of compounds 1 and 2.     

In vitro release of angiotensin-converting enzyme inhibitors, peroxyl-radical scavengers and antibacterial compounds by enzymatic hydrolysis of glycated gluten

The combined effect of gluten glycation and proteolysis on the release of compounds exhibiting in vitro angiotensin-converting enzyme (ACE) inhibitory, antioxidant and antibacterial activities was investigated. Model systems consisting of wheat gluten and glucose were heated at 120 °C for 45 min, 150 °C for 30 min and 220 °C for 30 min to produce various Maillard reaction products mimicking reactions occurring in bread crusts. Progress of the Maillard reaction was estimated through indirect measurement of Amadori compounds as 2-furoylmethyl-amino acids. Glycation was followed by digestion with Pronase E and ultrafiltration. The anti-hypertensive activity was measured as the ability to inhibit the activity of angiotensin I-converting enzyme involved in hypertension regulation. The Oxygen Radical Absorbance assay was used to measure the peroxyl radical scavenging capacity of the products and their effect on microbial growth of Escherichia coli ATCC 25922 and Staphlococcus aureus ATCC 25923 was also studied. Advanced products of the reaction enhanced the antioxidant and antibacterial properties of gluten hydrolysates and decreased the overall ACE inhibitory activity. Ultrafiltration provided a useful method for separating compounds (< 3000 Da) with ACE inhibitory activity and advanced Maillard reaction products (>3000 Da) which scavenged peroxyl radicals and inhibited the microbial growth.     

Pigmentation, carotenoids, lipid peroxides and lipid composition of skin of red porgy (Pagrus pagrus) fed diets supplemented with different astaxanthin sources

A feeding experiment was carried out to determine the efficiency of different commercial sources, chemical forms and levels, of dietary astaxanthin, to appropriately pigment the red porgy (Pagrus pagrus) skin. According to this, total carotenoid content, profiles and chemical forms present in the skin were determined. In order to establish the potential for antioxidant protecting role of astaxanthin supplemented diets, peroxide levels and lipid composition of skin were also determined.

Red porgy alevins were fed six dietary treatments in triplicate; a basal diet (B) without carotenoids; two diets (N25 and N50) formulated to supply either 25 or 50 mg kg^− 1 of an esterified source of astaxanthin (Haematococcus pluvialis, NatuRose™); two diets (CP25 and CP50) with either 25 or 50 mg kg^− 1 of unesterified astaxanthin (Carophyll® Pink); and a positive control diet (B + S) proved as a successful pigmenting-diet in previous experiences (B + S, 88% basal diet:12% frozen shrimp) [Cejas, J., Almansa, E., Tejera, N., Jerez, S., Bolaños, A., Lorenzo, A., 2003. Effect of dietary supplementation with shrimp on skin pigmentation and lipid composition of red porgy (P. pagrus) alevins. Aquaculture 218, 457–469].

All fish fed carotenoid supplemented diets displayed a pink-coloured skin after 4 months of feeding in contrast to the greyish appearance displayed by fish fed the basal diet not supplemented with carotenoids (B). Furthermore, astaxanthin diesters were the major carotenoid in the skin of pink fish. A second carotenoid, tentatively identified as tunaxanthin diester, was also detected. The best results in terms of skin natural reddish hue, total carotenoid and astaxanthin contents were found by using the esterified forms of dietary astaxanthin (N25, N50 and B + S). Interestingly, the lowest levels of lipid peroxides were found in the fish fed these three treatments. However, no effect of treatment on lipid composition was found. In conclusion, red porgy alevins are able to efficiently utilise dietary natural or synthetic astaxanthin, and deposit this pigment in its esterified form to acquire an acceptable pink-coloured skin compared to that of the wild fish.