Major constituents of the extracts from five green vegetables (broccoli, cabbage, spinach, brussels sprouts, kale), several of which are members of the genus Brassica (Cruciferous), have been separated by high-performance liquid chromatography (HPLC) on a C-18 reversed-phase column. Three classes of compounds were shown to be present. In the order of chromatographic elution, these were xanthophylls, chlorophylls and their derivatives, and the hydrocarbon carotenoids (carotenes). The xanthophylls were identified as neoxanthin, violaxanthin, lutein epoxide, and lutein. Several mono cis isomers of xanthophylls were also shown to be present in the extracts from these vegetables. The chlorophylls were identified as chlorophylls b and a and their decomposition products pheophytins b and a. The only hydrocarbon carotenoids present in these vegetables were all-trans-ß-caiotene and its 15,15'-cis isomer. j3-Apo-8'-carotenal and decapreno-/3-carotene have been employed respectively as internal standards for quantification of xanthophylls and carotenes. The effect of cooking on the qualitative and quantitative distribution of carotenoids in some of the vegetables has been discussed.

Abstract. We investigated the potential of red algae cultivated with deep-sea water (D) as dietary anti-oxidants to ameliorate the redox levels in the main organs and in bone metabolism using SAMP1 and its control SAMR1, in comparison with the same algae cultivated with surface seawater. Only the D group showed marked increases of glutathione (GSH) levels in the liver (R1, 134%) and brain (R1, 128% and P1, 126%) as well as activities of GSH non-dependent peroxidase in the liver (R1, 138%) and the brain (R1, 117% and P1, 112%) but not GSH-dependent peroxidase. The D diet also exhibited beneficial effects on bone metabolism; elevations of femoral calcium, phosphorus, hydroxyproline for collagen, hexosamine for polysaccharides, and suppression of urinary excretion of hydroxyproline as an index of increased bone resorption. A three-point bending test showed that the D diet increased the stiffness and the strength of the femur, which correlated with increases in femoral calcium and phosphorus contents. The results suggest that red algae of the Gracilaria sp. cultivated with deep-sea water has the potential to ameliorate degenerative diseases of aging. D

Two new polycyclic guanidine alkaloids, crambescidin 826 (1) and dehydrocrambine A (2), and the known compounds crambescidin 800 (3) and fromiamycalin (4) were isolated from the marine sponge Monanchora sp. The structures of 1 and 2 were elucidated by 2D NMR and mass spectrometry, and relative stereochemistry was established by analysis of coupling constants and ROESY spectra. The pentacyclic guanidine alkaloids 1, 3, and 4 inhibit HIV-1 envelope-mediated fusion in vitro with IC(50)'s of 1-3 microM, while compound 2, a tricyclic guanidine alkaloid, showed weaker inhibition, with an IC(50) of approximately 35 microM.

Forty alkaloids were detected and characterized from skin extracts of high- and low-elevation populations of the poison frog Dendrobates histrionicus from northwestern Colombia. Combined gc/ms with NH3 or ND3 in a chemical ionization mode detected protonated parent ions and determined the number of exchangeable NH and OH hydrogens. Six previously unknown dendrobatid alkaloids were characterized. Two were 2,5-disubstituted pyrrolidines, which included pyrrolidine 197B, a trans-2-butyl-5-pentylpyrrolidine, while a third was a 2,6-dipentylpiperidine. Indolizidines 239AB and 239CD had the same relative configuration as the parent alkaloid 223AB [(5E,9E)3-butyl-5-propylindolizidine] and contained, respectively, a omega-hydroxy group in the propyl or butyl side chain. The profiles of alkaloids in the new northern populations of D. histrionicus are typical of the species in containing a set of about eight histrionicotoxins, in marked contrast to a related species, Dendrobates lehmanni, which does not contain histrionicotoxins.

No abstract

The interaction of DNA with crystalline silica in buffered aqueous solutions at physiologic pH has been investigated by Fourier-transform infrared spectroscopy (FT-IR). In aqueous buffer, significant changes occur in the spectra of DNA and silica upon coincubation, suggesting that a DNA-silica complex forms as silica interacts with DNA. As compared to the spectrum of silica alone, the changes in the FT-IR spectrum of silica in the DNA-silica complex are consistent with an Si-O bond perturbation on the surface of the silica crystal. DNA remains in a B-form conformation in the DNA-silica complex. The most prominent changes in the DNA spectrum occur in the 1225 to 1000 cm1 region. Upon binding, the PO_ asymmetric stretch at 1225 cm1 is increased in intensity and slightly shifted to lower frequencies; the PO-symmetric stretch at 1086 cm1 is markedly increased in intensity; and the band at 1053 cm-, representing either the phosphodiester or the C-O stretch of DNA backbone, is significantly reduced in intensity.In D20 buffer, the DNA spectrum reveals a marked increase in intensity of the peak at 1086 cm-1 and a progressive decrease in intensity of the peak at 1053 cm-1 when DNA is exposed to increasing concentrations of silica. The carbonyl band at 1688 cm-diminishes and shifts to slightly lower frequencies with increasing concentrations of silica. The present study demonstrates that crystalline silica binds to the phosphate-sugar backbone of DNA. The close proximity of the silica surface to the DNA molecule, brought about by this binding, may contribute to DNA strand breakage produced by silica-derived free radicals. The ability of silica to form stable complexes with DNA may play an important role in the mechanisms of silica-induced toxicity and carcinogenesis. -Environ Health Perspect 102(Suppl 10):1 65-171 (1994)

We investigated the potential of red algae cultivated with deep-sea water (D) as dietary anti-oxidants to ameliorate the redox levels in the main organs and in bone metabolism using SAMP1 and its control SAMR1, in comparison with the same algae cultivated with surface seawater. Only the D group showed marked increases of glutathione (GSH) levels in the liver (R1, 134%) and brain (R1, 128% and P1, 126%) as well as activities of GSH non-dependent peroxidase in the liver (R1, 138%) and the brain (R1, 117% and P1, 112%) but not GSH-dependent peroxidase. The D diet also exhibited beneficial effects on bone metabolism; elevations of femoral calcium, phosphorus, hydroxyproline for collagen, hexosamine for polysaccharides, and suppression of urinary excretion of hydroxyproline as an index of increased bone resorption. A three-point bending test showed that the D diet increased the stiffness and the strength of the femur, which correlated with increases in femoral calcium and phosphorus contents. The results suggest that red algae of the Gracilaria sp. cultivated with deep-sea water has the potential to ameliorate degenerative diseases of aging.

A series of phenylcarbamate analogues of geneserine (8, 10, 12, 14) were synthesized from their counterparts, the phenylcarbamate analogues of physostigmine (2-5), by oxidation. The geneserine analogues can undergo tautomerism between N-oxide and 1,2-oxazine structures in a pH- and time-dependent manner. Assessment by (1)H NMR indicated that the N-oxide structure is adopted at neutral pH and that the compound exists in an equilibrium between several epimers. Evaluation of their biological action to inhibit human acetylcholinesterase (AChE) and butyrylcholinesterase (BChE), ex vivo, demonstrated that the N-oxide (7, 9, 11, 13, 15) and 1,2-oxazine (6, 8, 10, 12, 14) structures possessed similar potencies against AChE, but the latter structures were more potent against BChE. With the exception of the BChE selective inhibitor, 12, none of the geneserine analogues were as potent or enzyme subtype selective as their physostigmine analogue counterparts.