Comparison of negative and positive ion electrospray tandem mass spectrometry for the liquid chromatography tandem mass spectrometry analysis of oxidized deoxynucleosides

AbstractOxidized deoxynucleosides are widely used as biomarkers for DNA oxidation and oxidative stress assessment. Although gas chromatography mass spectrometry is widely used for the measurement of multiple DNA lesions, this approach requires complex sample preparation contributing to possible artifactual oxidation. To address these issues, a high performance liquid chromatography (HPLC)-tandem mass spectrometric (LC-MS/MS) method was developed to measure 8-hydroxy-2′-deoxyguanosine (8-OH-dG), 8-hydroxy-2′-deoxyadenosine (8-OH-dA), 2-hydroxy-2′-deoxyadenosine (2-OH-dA), thymidine glycol (TG), and 5-hydroxymethyl-2′-deoxyuridine (HMDU) in DNA samples with fast sample preparation. In order to selectively monitor the product ions of these precursors with optimum sensitivity for use during quantitative LC-MS/MS analysis, unique and abundant fragment ions had to be identified during MS/MS with collision-induced dissociation (CID). Positive and negative ion electrospray tandem mass spectra with CID were compared for the analysis of these five oxidized deoxynucleosides. The most abundant fragment ions were usually formed by cleavage of the glycosidic bond in both positive and negative ion modes. However, in the negative ion electrospray tandem mass spectra of 8-OH-dG, 2-OH-dA, and 8-OH-dA, cleavage of two bonds within the sugar ring produced abundant S1 type ions with loss of a neutral molecule weighing 90 u, [M − H − 90]−. The signal-to-noise ratio was similar for negative and positive ion electrospray MS/MS except in the case of thymidine glycol where the signal-to-noise was 100 times greater in negative ionization mode. Therefore, negative ion electrospray tandem mass spectrometry with CID would be preferred to positive ion mode for the analysis of sets of oxidized deoxynucleosides that include thymidine glycol. Investigation of the fragmentation pathways indicated some new general rules for the fragmentation of negatively charged oxidized nucleosides. When purine nucleosides contain a hydroxyl group in the C8 position, an S1 type product ion will dominate the product ions due to a six-membered ring hydrogen transfer process. Finally, a new type of fragment ion formed by elimination of a neutral molecule weighing 48 (CO2H4) from the sugar moiety was observed for all three oxidized purine nucleosides

Stranger to Familiar: Wild Strepsirhines Manage Xenophobia by Playing

The power of play in limiting xenophobia is a well-known phenomenon in humans. Yet, the evidence in social animals remains meager. Here, we aim to determine whether play promotes social tolerance toward strangers in one of the most basal group of primates, the strepsirhines. We observed two groups of wild lemurs (Propithecus verreauxi, Verreaux's sifaka) during the mating season. Data were also collected on nine visiting, outgroup males. We compared the distribution of play, grooming, and aggressive interactions across three conditions: OUT (resident/outgroup interactions), IN (resident/resident interactions in presence of outgroups) and BL-IN (baseline of resident/resident interactions in absence of outgroups). Play frequency between males was higher in OUT than in IN and BL-IN conditions; whereas, grooming was more frequent in IN than in OUT and BL-IN conditions. Aggression rates between resident and outgroup males were significantly higher than those between residents. However, aggressions between resident and outgroup males significantly decreased after the first play session and became comparable with resident-resident aggression levels. The presence of strangers in a well-established group implies the onset of novel social circumstances, which sifaka males cope with by two different tactics: grooming with ingroup males and playing with outgroup ones. The grooming peak, concurrently with the visit of outgroups, probably represents a social shield adopted by resident males to make their pre-existing affiliation more evident to the stranger “audience”. Being mostly restricted to unfamiliar males, adult play in sifaka appears to have a role in managing new social situations more than in maintaining old relationships. In particular, our results indicate not only that play is the interface between strangers but also that it has a specific function in reducing xenophobia. In conclusion, play appears to be an ice-breaker mechanism in the critical process that “upgrades” an individual from stranger to familiar

Primate social cognition: uniquely primate, uniquely social, or just unique?

Primates undoubtedly have impressive abilities in perceiving, recognising, understanding and interpreting other individuals, their ranks and relationships; they learn rapidly in social situations, employ both deceptive and cooperative tactics to manipulate companions, and distinguish others’ knowledge from ignorance. Some evidence suggests that great apes recognize the cognitive basis of manipulative tactics and have a deeper appreciation of intention and cooperation than monkeys; and only great apes among primates show any understanding of the concept of self. None of these abilities is unique to primates, however. We distinguish (1) a package of quantitative advantages in social sophistication, evident in several broad mammalian taxa, in which neocortical enlargement is associated with social group size; from (2) a qualitative difference in understanding found in several distantly related but large-brained species, including great apes, some corvids, and perhaps elephants, dolphins, and domestic dogs. Convergence of similar abilities in widely divergent taxa should enable their cognitive basis and evolutionary origins to be determined. Cortical enlargement seems to have been evolutionarily selected by social challenges, although it confers intellectual benefits in other domains also; most likely the mechanism is more efficient memory. The taxonomic distribution of qualitatively special social skills does not point to an evolutionary origin in social challenges, and may be more closely linked to a need to acquire novel ways of dealing with the physical world; but at present research on this question remains in its infancy. In the case of great apes, their ability to learn new manual routines by parsing action components may also account for their qualitatively different social skills, suggesting that any strict partition of physical and social cognition is likely to be misleading

La política exterior de los Estados Unidos y el desarrollo del Tercer Mundo

What are the main guidelines and consequences of the current policy of the United States towards Latin America? What would be required to steer policy in a direction that would be most beneficial for the development of Latin America? The questions invite a thorough critique of current practices and an examination of national requirements or preconditions for accelerated development and the general role of the US as an obstruction to structural changes that would allow for faster development in the Third World. By definition, any set of US foreign policies that are more compatible with Third World development will have to include a much larger proportion of actions of consideration to others than the current self-consideration ones.¿Cuáles son los lineamientos y las consecuencias primordiales de la política actual de los Estados Unidos hacia Latinoamérica? ¿Que se requeriría para orientar Ia política en una dirección que resultara más beneficiosa para el desarrollo de América Latina? Las preguntas invitan a una crítica minuciosa de las prácticas actuales y a un examen de los requisitos nacionales o las precondiciones del desarrollo acelerado y el papel general de los EE.UU. como obstrucción para los cambios estructurales que permitirían el desarrollo más rápido en el Tercer Mundo. Por definición, cualquier conjunto de políticas exteriores de los Estados Unidos que resulte más compatible con el desarrollo del Tercer Mundo tendrá que incluir una proporción mucho más grande de acciones de consideración a otros, en comparación con las de auto consideración de la actual