The reactivity of carotenoid radicals with oxygen

The possibility that carotenoid radicals react with oxygen to form chain-carrying peroxyl radicals has been postulated to account for the reduction in antioxidant effetiveness displayed by some carotenoids at high oxygen concentrations. The primary objective of the work described in this paper was to measure the rate constants for oxygen addition to a series of carotenoid radicals and to examine any influence of carotenoid structural features on these rate constants. Laser flash photolysis has been used to generate long-lived carotenoid radicals (PhS-CAR^√) derived from radical addition reactions with phenylthiyl radicals (PhS^√) in benzene. The PhS-CAR^√ radicals are scavenged by oxygen at rates that display a moderate dependence on the number of conjugated double bonds (n_db) in the carotenoid. The rate constants range from ∼10³ to ∼10⁴ M^- 1 s^- 1 for n_db = 7-11. The data also suggest that the presence of terminal cyclic groups may cause an increase in the rate constant for oxygen addition.     

Probing inter-ligand excited state interaction in homo and heteroleptic ruthenium(II) polypyridyl complexes using selective deuteriation

The effect of deuteriation on the photophysical properties of two series of regioselectively deuteriated Ru(II) complexes ([Ru(bipy)_x(ph₂phen)_3−x]²⁺, where x = 0-3 and ph₂phen is 4,7-diphenyl-1,10-phenanthroline and [Ru(bipy)₂(dcbipy²⁻)], where H₂dcbipy is 4,4′-dicarboxy-2,2′-bipyridyl) is reported. Although overall, deuteriation results in an increase in emission lifetime for all complexes, the effect of substitution of hydrogen for deuterium shows strong regioselectivity both in terms of the ligand and the position on individual ligands that are exchanged.     

Analysis of five y-Specific microsatellite loci in Asian and Pacific populations

We have analyzed five Y-specific microsatellite loci (DYS388, DYS390, DYS391, DYS394, DYS395) in 17 Asian and Pacific populations representing a broad geographical area and different linguistic families, with an emphasis on populations from mainland and insular Southeast Asia. Analysis of gene diversity indicates that several of the studied populations have experienced substantial genetic isolation, and a reduction in male effective sizes (viz. the Northeast Indian populations Nishi, Adi and the Taiwanese aboriginals). The average values of the F_ST and (_ST statistics indicate a high degree of genetic differentiation among these populations at the five Y-specific markers (F_ST =0.21 and (_ST = 0.33, based on individual loci; F_ST = 0.09 and (_ST = 0.36, based on haplotypes), which conform to the expectation of a fourfold smaller effective size of the Y-linked loci compared with the autosomal loci. Dendrogram and principal coordinates analysis, with few exceptions, show a major separation between mainland and insular populations. Among the mainland populations, the Tibeto-Burman speakers from Northeast India cluster in a well-defined group, supported by high bootstrap values. The Southern Chinese, Northern Thai, So, and Cambodian also are integral to this cluster. The other major cluster is rather heterogeneous and includes, among others, the Austronesian-speaking populations. The Samoans of the Pacific, with a distinctive pattern of allelic distributions, stand as an outlier in the tree and PC representations. Although trends of genetic affinities among ethnically and geographically related populations are evident from the Y-specific microsatellite data, microsatellites are not optimal for deciphering complex migratory patterns of human populations, which could possibly be clarified by using additional and more stable genetic markers. Am J Phys Anthropol 110: 1–16, 1999. © 1999 Wiley-Liss, Inc.     

Genetic variation at 9 autosomal microsatellite loci in Asian and Pacific populations.

Genetic variation at 9 autosomal microsatellite loci (CFS1R, TH01, PLA2A, F13A1, CYP19, LPL, D20S481, D20S473, and D20S604) has been characterized in 16 Asian and Oceanic populations, mostly from mainland and insular Southeast Asia. The neighbor-joining tree and the principal coordinates analysis of the genetic relationships of these populations show a clear separation of Papua New Guinea Highlanders and, to a lesser extent, Malayan aborigines (Orang Asli or Semai) from the rest of the populations. Although the number of markers used in this study appears to be inadequate for clarifying the patterns of genetic relationships among the studied populations, in the principal coordinates analysis a geographic trend is observed in the mainland and insular Southeast Asian populations. Furthermore, in an attempt to contrast the extent of variation between autosomal and Y-chromosome-specific microsatellite loci and to reveal potential differences in the patterns of male and female migrations, we have also compared genetic variation at these 9 autosomal loci with variation observed at 5 Y-chromosome-specific microsatellites in a common set of 14 Asian populations.     

Molecular dynamics study of the KcsA potassium channel

The structural, dynamical, and thermodynamic properties of a model potassium channel are studied using molecular dynamics simulations. We use the recently unveiled protein structure for the KcsA potassium channel from Streptomyces lividans. Total and free energy profiles of potassium and sodium ions reveal a considerable preference for the larger potassium ions. The selectivity of the channel arises from its ability to completely solvate the potassium ions, but not the smaller sodium ions. Self-diffusion of water within the narrow selectivity filter is found to be reduced by an order of magnitude from bulk levels, whereas the wider hydrophobic section of the pore maintains near-bulk self-diffusion. Simulations examining multiple ion configurations suggest a two-ion channel. Ion diffusion is found to be reduced to approximately (1)/(3) of bulk diffusion within the selectivity filter. The reduced ion mobility does not hinder the passage of ions, as permeation appears to be driven by Coulomb repulsion within this multiple ion channel.     

Basement membrane complexes with biological activity

We have studied the reconstitution of basement membrane molecules from extracts prepared from the basement membrane of the EHS tumor. Under physiological conditions and in the presence of added type IV collagen and heparan sulfate proteoglycan, gellike structures form whose ultrastructure appears as interconnected thin sheets resembling the lamina dense zone of basement membrane. The major components of the reconstituted structures include laminin, type IV collagen, heparan sulfate proteoglycan, entactin, and nidogen. These components polymerize in constant proportions on reconstitution, suggesting that they interact in defined proportions. Molecular sieve studies on the soluble extract demonstrate that laminin, entactin, and nidogen are associated in large but dissociable complexes which may be a necessary intermediate in the deposition of basement membrane. The reconstituted matrix was biologically active and stimulated the growth and differentiation of certain cells.     

Nematostatic Activity of Oxamyl and N,N-Dimethyl-1-cyanoformamide (DMCF) on Meloidogyne incognita Juveniles

The nematostatic activity of oxamyl, methyl-N'',N''-dimethy]-N-hydroxy-l-thiooxamimidate (oxamyl-oxime) and N,N-dimethyl-l-cyanoformamide (DMCF) was studied by immersing 10 Meloidogyne incognita second-stage juveniles into aqueous solutions of various concentrations of each chemical. At concentrations of 500 to 8,000 μg/ml, oxamyl quickly immobilized immersed juveniles. In all other concentrations studied (down to 4 μg/ml), oxamyl stopped or reduced movement of juveniles within 24 hours. DMCF also quickly immobilized juveniles at concentrations of 4,000 and 8,000 μg/ml and reduced movement at 2,000 μg/ml. Lower concentrations had no observed effect on movement. In solutions of the oxime from 2,000 to 8,000 μg/ml, some reduction of movement was observed, but most juveniles maintained some motion over a period of 24 hours. Juveniles were transferred to water from 4,000 μg/ml solutions of oxamyl and DMCF after various intervals of time in order to determine the effect of duration of exposure to the chemicals on the ability of the immobilized juveniles to recover normal motion. Some recovery was observed even after 24 hours of exposure to DMCF, but none after exposure to oxamyl for longer than 40 minutes.     

Evolutionary history of the COII/tRNALys intergenic 9 base pair deletion in human mitochondrial DNAs from the Pacific

Length changes in human mitochondrial DNA (mtDNA) are potentially useful markers for inferring the evolutionary history of populations. One such length change is a nine base pair (9-bp) deletion that is located in the intergenic region between the COII gene and the Lysine tRNA gene (COII/tRNALys intergenic region). This deletion has been used as a genetic marker to trace descent from peoples of East Asian origin. A geographic cline of the deletion frequency across modern Pacific Islander populations suggests that the deletion may be useful for tracing prehistoric Polynesian origins and affinities. Mitochondrial DNA sequence variation within two variable segments of the control region (CR) permits a number of inferences regarding the evolutionary history of the 9-bp deletion that cannot be determined from frequency data alone. We obtained CR sequences from 74 mtDNAs with the 9-bp deletion from Indonesia, coastal Papua New Guinea (PNG), and American Samoa. Phylogenetic and pairwise distribution analysis of these CR sequences pooled with previously published CR sequences reveals that the deletion arose independently in Africa and Asia and suggests possible multiple origins of the deletion in Asia. A clinal increase of the frequency of the 9-bp deletion across the three Pacific populations is associated with a decrease in CR sequence diversity, consistent with founder events. Furthermore, analysis of pairwise difference distributions indicates an expansion time of proto-Polynesians that began 5,500 yr ago from Southeast Asia. These results are consistent with the express train model of Polynesian origins.