RESUMO
We report the first conductance measurements of [n]staffane oligomers in single-molecule junctions. Our studies reveal two quantum transport characteristics unique to staffanes that emerge from their strained bicyclic structure. First, though staffanes are composed of weakly conjugated C-C σ-bonds, staffanes carry a shallower conductance decay value (ß = 0.84 ± 0.02 n-1) than alkane chain analogs (ß = 0.96 ± 0.03 n-1) when measured with the scanning tunneling microscopy break junction (STM-BJ) technique. Staffanes are more conductive than other σ-bonded organic backbones in the literature on a per atom basis. Density functional theory calculations suggest staffane backbones are effective conduits for charge transport because their significant bicyclic ring strain destabilizes the HOMO-2 energy, aligning it more closely with the Fermi energy as oligomer order increases. Second, the monostaffane is significantly lower conducting than expected. DFT calculations suggest that short monostaffanes sterically enforce insulating gauche interelectrode orientations over syn orientations. Meanwhile, [2-5]staffane wires may accommodate axial mechanical strain by "rod-bending". These findings show for the first time how bicyclic ring strain can enhance charge transmission in saturated molecular wires. These studies showcase the STM-BJ technique as a valuable tool for uncovering the stereoelectronic proclivities of molecules at material interfaces.
RESUMO
The D-loop region on mitochondrial DNA (mtDNA) is frequently used for analyses of maternal lineages within domestic animal species. There are many native pig breeds in Vietnam, but their origins remain unclear. This study investigated maternal lineages using the D-loop region on mtDNA of 260 samples collected from native pigs in 20 provinces across Vietnam. The D-loop region of all samples was amplified and sequenced. We obtained 713 bp sequences of the D-loop region for each sample excluding the repeat region, and variants on this region were used to construct a phylogenetic tree. We detected 50 haplotypes from Vietnamese native pigs, with 27 novel haplotypes. Phylogenetic tree analysis showed two haplotype groups: one for the MTSEA group, frequently found in domestic pigs in the mountainous areas of Cambodia and Laos; and the D2 group, found in pigs originating from Chinese pigs. No European haplotype was found. Haplotypes in northeast Vietnam comprised only haplotypes of the D2 group, whereas in areas from the northwest mountains to the south, we found haplotypes belonging to both the D2 and MTSEA groups. This study suggested that both origins contributed to maternal lineages of current populations of Vietnamese native pigs.
Assuntos
DNA Mitocondrial , Variação Genética , Animais , DNA Mitocondrial/genética , Haplótipos/genética , Filogenia , Sus scrofa/genética , Suínos/genética , VietnãRESUMO
A voltammetric study of a series of alkyl and aryl S-glucosides unveiled the reactivity patterns of alkyl S-glucosides toward anodic oxidation and found noteworthy differences with the trends followed by aryl derivatives. The oxidation potential of alkyl S-glucosides, estimated herein from square-wave voltammetry peak potentials (Ep), depends on the steric properties of the aglycone. Glucosides substituted with bulky groups exhibit Ep values at voltages more positive than the values of those carrying small aglycones. This relationship, observed in all analyzed alkyl series, is evidenced by good linear correlations between Ep and Taft's steric parameters (ES) of the respective alkyl substituents. Moreover, the role of the aglycone's steric properties as a primary reactivity modulator is backed by poor correlations between Ep and the radical stabilization energies (RSEs) of the aglycone-derived thiyl radicals (RSâ¢). In contrast, aryl glucosides' Ep values exhibit excellent correlations with the aryl substituents' Hammett parameters (σ+) and the ArS⢠RSEs, evidencing the inherent stability of the reactive radical intermediate as the primary factor controlling aryl glucoside's electrochemical reactivity. The reactivity differences between alkyl and aryl S-glucosides also extend to the protective group's effect on Ep. Alkyl S-glucosides' reactivity proved to be more sensitive to protective group exchange.
Assuntos
Glucosídeos , Eletrodos , OxirreduçãoRESUMO
We have elucidated genetic relationships of Vietnamese native pigs (VNP) using preliminarily collected samples by a single-nucleotide polymorphism (SNP) array. In order to confirm our previous results and compare with the results of a previous study using microsatellite (MS) markers, we aimed to characterize genetic diversity and population structure in wider varieties (24 breeds from 21 Provinces) of VNP across the country using 20 polymorphic MS markers recommended by ISAG/FAO (International Society for Animal Genetics/Food and Agriculture Organization) for diversity study. In this study, we collected 1,136 DNA samples of the VNPs and three exotic breeds. Our results revealed that the average number of alleles and allelic richness across the loci in VNPs were 10.0 and 7.6, which were higher than those of exotic breeds. Genomic components among VNPs were subjected to the sampling locations. Interestingly, Co Binh Thuan showed remarkable genetic feature compared to the other VNPs, because the habitation of Co Binh Thuan was relatively far from the other breeds. The results of this study provided useful information for exploitation, conservation, and development trends of the VNP breeds. More recently, African swine fever caused significant damage to most of the VNP populations. Therefore, our findings will help a reconstruction scheme of the VNP genetic resources.