Fragmentation studies and electrospray ionization mass spectrometry of lapachol: protonated, deprotonated and cationized species

Electrospray ionization mass spectrometric analysis of lapachol (2-hydroxy-3-(3-methy1-2-butenyl)-1,4-naphthoquinone) was accomplished in order to elucidate the gas-phase dissociation reactions of this important biologically active natural product. The occurrence of protonated and cationized species in the positive mode and of deprotonated species in the negative mode was explored by means of collision-induced dissociation (CID) experiments. For the protonated molecule, the H(2)O and C(4)H(8) losses occur by two competitive channels. For the deprotonated molecule, the even-electron rule is not conserved, and the radicalar species are eliminated by formation of distonic anions. The fragmentation mechanism for each ion was suggested on the basis of computational thermochemistry. Atomic charges, relative energies, and frontier orbitals were employed aiming at a better understanding of the gas-phase reactivity of lapachol. Potential energy surfaces for fragmentation reactions were obtained by the B3LYP/6-31+G(d,p) model. Copyright (C) 2010 John Wiley & Sons, Ltd.

Interference pattern with a dark center from two atoms driven by a coherent laser field

In a recent paper Meyer and Yeoman [Phys. Rev. Lett. 79, 2650 (1997)] have shown that the resonance fluorescence from two atoms placed in a cavity and driven by an incoherent field can produce an interference pattern with a dark center. We study the fluorescence from two coherently driven atoms in free space and show that this system can also produce an interference pattern with a dark center. This happens when the atoms are in nonequivalent positions in the driving: field, i.e., the atoms experience different intensities and phases of the driving field. We discuss the role of the interatomic interactions in this process and find that the interference pattern with a dark center results from the participation of the antisymmetric state in the dynamics of the driven two-atom system.

Interference pattern with a dark center in resonance fluorescence from two atoms driven by a squeezed vacuum field

We study the resonance fluorescence from two interacting atoms driven by a squeezed vacuum field and show that this system produces an interference pattern with a dark center. We discuss the role of the interatomic interactions in this process and find that the interference pattern results from an unequal population of the symmetric and antisymmetric states of the two-atom system. We also identify intrinsically nonclassical effects versus classical squeezed field effects, (C) 1998 Elsevier Science B.V. All rights reserved.

Percolative fragmentation of char particles during gasification

Percolative fragmentation was confirmed to occur during gasification of three microporous coal chars. Indirect evidence obtained by the variation of electrical resistivity (ER) with conversion was supported by direct observation of numerous fragments during gasification. The resistivity increases slowly at low conversions and then sharply after a certain conversion value, which is a typical percolation phenomenon suggesting the occurrence of internal fragmentation at high conversion. Two percolation models are applied to interpret the experimental data and determine the percolation threshold. A percolation threshold of 0.02-0.07 was found, corresponding to a critical conversion of 92-96% for fragmentation. The electrical resistivity variation at high conversions is found to be very sensitive to diffusional effects during gasification. Partially burnt samples with a narrow initial particle size range were also observed microscopically, and found to yield a large number of small fragments even when the particles showed no disintegration and chemical control prevailed. It is proposed that this is due to the separation of isolated clusters from the particle surface. The particle size distribution of the fragments was essentially independent of the reaction conditions and the char type, and supported the prediction by percolation theory that the number fraction distribution varies linearly with mass in a log-log plot. The results imply that perimeter fragmentation would occur in practical combustion systems in which the reactions are strongly diffusion affected.

Cell death and immunohistochemistry of p53, c-Fos and c-Jun after spermine infection into the rat striatum

Administration of polyamines into the central nervous system results in tissue damage, possibly through the excitotoxic actions of the NMDA receptor. Direct injection of 100 nmol of spermine into the rat striatum produced a lesion equivalent to approximately 50% of the striatum. Analysis of the DNA in this region revealed the distinct ladder-like pattern of degradation often associated with apoptosis. This DNA fragmentation was confirmed in vivo using terminal deoxynucleotidyl-transferase-mediated biotinylated deoxyuridine triphosphate nick end labelling (TUNEL). The morphology of the TUNEL-positive cells showed marked differences at the needle tract when compared with cells in damaged areas away from the needle tract, suggesting a differential mechanism of cell death in these two regions. The patterns of p53, c-Fos and c-Jun protein expression were determined using immunohistochemistry. The number of p53-immunoreactive cells increased up to 14 h and returned to basal levels by 24 h. c-Fos protein expression transiently increased, peaking at 8 h after injection, c-Jun exhibited a protracted pattern of expression, remaining elevated up to 24 h. p53 protein expression was colocalised with TUNEL staining in areas away from the needle tract, but not in cells at the needle tract, suggesting once again a differential mechanism of cell death. At 14 h, c-Fos and c-Jun were not colocalised with TUNEL staining, suggesting that they are either not involved with the cell death process or that the time course of protein expression and the onset of DNA fragmentation do not overlap. This work represents the first characterisation of processes associated with cell death induced by spermine in vivo.

Incubation of eggs of the Australian broad-shelled turtle, Chelodina expansa (Testudinata : Chelidae), at different temperatures: effects on pattern of oxygen consumption and hatchling morphology

Incubation temperature influences embryonic development and the morphology of resultant hatchlings in many species of turtle but few studies have addressed its effect on oxygen consumption and total embryonic energy expenditure. Eggs of the Australian broad-shelled river turtle, Chelodina expansa, were incubated at constant temperatures of 24 degrees C and 28 degrees C to determine the effect of temperature on oxygen consumption, embryonic energy expenditure and hatchling morphology. All embryos at both incubation temperatures experienced a period of developmental diapause immediately after oviposition. Once this initial diapause was broken, embryos underwent a further period of developmental arrest when the embryo was still very small and had minimal oxygen consumption (

Spatial and temporal variation in distribution of mangroves in Moreton Bay, subtropical Australia: a comparison of pattern metrics and change detection analyses based on aerial photographs

An assessment of the changes in the distribution and extent of mangroves within Moreton Bay, southeast Queensland, Australia, was carried out. Two assessment methods were evaluated: spatial and temporal pattern metrics analysis, and change detection analysis. Currently, about 15,000 ha of mangroves are present in Moreton Bay. These mangroves are important ecosystems, but are subject to disturbance from a number of sources. Over the past 25 years, there has been a loss of more than 3800 ha, as a result of natural losses and mangrove clearing (e.g. for urban and industrial development, agriculture and aquaculture). However, areas of new mangroves have become established over the same time period, offsetting these losses to create a net loss of about 200 ha. These new mangroves have mainly appeared in the southern bay region and the bay islands, particularly on the landward edge of existing mangroves. In addition, spatial patterns and species composition of mangrove patches have changed. The pattern metrics analysis provided an overview of mangrove distribution and change in the form of single metric values, while the change detection analysis gave a more detailed and spatially explicit description of change. An analysis of the effects of spatial scales on the pattern metrics indicated that they were relatively insensitive to scale at spatial resolutions less than 50 m, but that most metrics became sensitive at coarser resolutions, a finding which has implications for mapping of mangroves based on remotely sensed data. (C) 2003 Elsevier Science B.V. All rights reserved.

Fragmentation of a Neotropical migratory fish population by a century-old dam

Loss of connectivity in impounded rivers is among the impacts imposed by dams, and mitigation measures such as fish passages might not accomplish their purpose of reestablishing an efficient bi-directional gene flow in the fish populations affected. As a consequence, fish populations remain fragmented, and a new interpopulational structure may develop, with increased risk of reduced genetic diversity and stochastic extinction. In order to evaluate the effects of the Gavio Peixoto Dam, which was constructed almost a century ago on the Jacar,-Gua double dagger u River in the Upper Parana River basin, Brazil, a comparative morphometric study was undertaken on the populations of the Neotropical migratory characid fish Salminus hilarii living up- and downstream of this dam. Population dynamics, spatial segregation, and habitat use by different age classes were monitored for 2 years. We found that segregation caused by the dam and long periods with no efficient connection by fish passages have led to fragmentation and interpopulational structuring of S. hilarii, as revealed by canonical variable analysis of morphometric features. The fish populations occupying the up- and downstream sections have succeeded in performing short-distance reproductive migrations in the main river and tributaries, have found suitable habitats for completing their life cycle, and have been able to maintain distinct small-sized populations so far.

Mitochondrial DNA Variability Among Eight Tikuna Villages: Evidence for an Intratribal Genetic Heterogeneity Pattern

To study the genetic structure of the Tikuna tribe, four major Native American mitochondrial DNA (mtDNA) founder haplogroups were analyzed in 187 Amerindians from eight Tikuna villages located in the Brazilian Amazon. The central position of these villages in the continent makes them relevant for attempts to reconstruct population movements in South America. In this geographic region, there is particular concern regarding the genetic structure of the Tikuna tribe, formerly designated ""enigmatic"" due to its remarkable degree of intratribal homogeneity and the scarcity of private protein variants. In spite of its large population size and geographic distribution, the Tikuna tribe presents marked genetic and linguistic isolation. All individuals presented indigenous mtDNA haplogroups. An intratribal genetic heterogeneity pattern characterized by two highly homogeneous Tikuna groups that differ considerably from each other was observed. Such a finding was unexpected, since the Tikuna tribe is characterized by a social system that favors intratribal exogamy and patrilocality that would lead to a higher female migration rate and homogenization of the mtDNA gene pool. Demographic explosions and religious events, which significantly changed the sizes and compositions of many Tikuna villages, may be reflected in the genetic results presented here. Am J Phys Anthropol 140:526-531,2009. (C) 2009 Wiley-Liss, Inc

What the reasons for no inbreeding and high genetic diversity of the neotropical fig tree Ficus arpazusa ?

Ficus arpazusa Casaretto is a fig tree native to the Atlantic Rain Forest sensu lato. High levels of genetic diversity and no inbreeding were observed in Ficus arpazusa. This genetic pattern is due to the action of its pollinator, Pegoscapus sp., which disperses pollen an estimated distance of 5.6 km, and of Ficus arpazusa`s mating system which, in the study area, is allogamous. This study highlights the importance of adding both ecological and genetic data into population studies, allowing a better understanding of evolutionary processes and in turn increasing the efficacy of forest management and revegetation projects, as well as species conservation.

Could the Leukocyte X Chromosome Inactivation Pattern Be Extrapolated to Hair Bulbs?

Background: The androgen receptor gene is located on the X chromosome with a polymorphic tract of CAG repeats that is inversely correlated to the receptor`s transactivation activity. A short CAG tract is associated with hyperandrogenic disorders. In women, one of the X chromosomes is inactivated and the X chromosome inactivation (XCI) pattern varies among tissues. Previous studies of hyperandrogenic disorders only evaluated XCI in leukocytes. Objective: To evaluate whether the XCI pattern in leukocytes could be extrapolated to those in hair bulbs. Material: A total of 58 healthy women were used for this study. DNA was extracted from leukocytes (n = 58 women) and pubic (n = 53 women) and scalp hair (n = 21 women). Methods: Hpa II digested and undigested DNA samples underwent fluorescence PCR GeneScan (R) analysis. Results: A significant and positive correlation of XCI was found between leukocytes and hair bulbs. However, individual comparisons showed that 13 and 19% of the women presented a different leukocyte XCI pattern in pubic hair and similar in leukocytes and hair bulbs of normal women indicating that leukocyte DNA is useful for XCI analysis. However, the XCI pattern could vary among tissues from the same subject, indicating that care should be taken when extrapolating individual leukocyte XCI patterns to other tissue. Copyright (C) 2010 S. Karger AG, Basel

Clinical changes of cervical dystonia pattern in long-term botulinum toxin treated patients

Cervical dystonia (CD) is a complex disorder but the response to long-term botulinum toxin (BTX) therapy is satisfactory in most cases. Bad results are attributed by some authors to changes in muscle activation. Our purpose is to verify if the change in head deviation affects negatively the response to BTX therapy it) a long-term follow-up, and if there are any differences in clinical parameters of these patients in comparison to those with stable pattern. From a total of 88 patients evaluated at the Movement Disorders Clinics of Hospital das Clinicas - University of Sao Paulo School of Medicine between January 1993 and December 2005, 67 were included. In 24 (35.8%) change in pattern of CID was observed, in a medium follow-up period of 80 months. The time between onset of dystonia and the diagnosis of pattern change was 9.7 years. Comparing with patients with no changes in CD pattern, there were no significant statistical differences. Improvement of symptoms around 60% was reported in both groups. In conclusion, the change in head deviation observed in CD was not responsible for bad response to therapy with BTX and there were no significant differences between both groups. (C) 2009 Elsevier Ltd. All rights reserved.

Is facial pattern a predisposing factor for otitis media with effusion in children?

Abnormalities in craniofacial morphology are associated with Eustachian tube dysfunction and otitis media with effusion (OME). Aim: to evaluate the relationship between facial pattern and craniofacial growth direction, and OME in children with enlarged tonsils and adenoids (ETA). Methods: Clinical prospective survey in 79 children (41 male and 38 female), ranging from 4 to 10 years of age, with tonsil and adenoid enlargement (Brodsky`s grades III and IV). Forty children presented with OME (study group) and 39 did not (control group). Cephalometric analysis was used to determine the facial pattern. Results: There was no correlation observed between facial pattern and OME (c 2 = 0.25 p = 0.88). Facial Axis was larger in the OME group (F(1.75) = 3.68 p = 0.05) and the Lower Anterior Facial height was smaller (F(1. 75) = 3.99 p = 0.05) in children with otitis media with effusion. Conclusions: There was no correlation between OME and facial pattern in children with ETA although a more horizontal facial growth direction, and a smaller lower anterior facial height was observed consistently among subjects in this group. This suggests that abnormal positioning of the eustachian tube influences the development of OME in children with ETA.

Spatial distribution of pink wax scale, Ceroplastes rubens Maskell (Hemiptera: Coccidae), on umbrella trees in south-eastern Queensland: The pattern of outbreaks

The spatial pattern of outbreaks of pink wax scale, Ceroplastes rubens Maskell, within and among umbrella trees, Schefflera actinophylla (Endl.), in southeastern Queensland was investigated. Pink wax scale was common on S. actinophylla, with approximately 84% of trees positive for scale and 14% of bees recording outbreak densities exceeding 0.4 adults per leaflet. Highly aggregated distributions of C. rubens occur within and among umbrella trees. Clumped distributions within trees appear to result from variable birth and death rates and limited movement of first instar crawlers. The patchy distribution of pink wax scale among trees is probably a consequence of variation in dispersal success of scale, host and environmental suitability for establishment and rates of biological control. Pink wax scale was more prevalent on trees in roadside positions and in exposed situations, indicating that such trees are more suitable and/or susceptible to scale colonisation.

Hyrax appliance opening and pattern of skeletal maxillary expansion after surgically assisted rapid palatal expansion: a computed tomography evaluation

Objective. The objective of this study was to evaluate, using computed tomography, correlations between Hyrax appliance opening and post-SARPE skeletal changes. Study design. Fifteen patients underwent SARPE according to a specific protocol and were followed. Linear and angular measurements of the anterior, intermediate, and posterior portions of the maxilla were evaluated. The correlation between maxillary expansion and appliance opening was investigated. Results. Significant overall expansion was observed. In the anterior and intermediate portions of the maxilla, the increase in maxillary width was greater than that observed in the posterior portion. The degree of appliance opening was significantly greater than that of the skeletal expansion. Also, no linear correlation between appliance opening and regional maxillary expansion was established. Conclusion. The transverse expansion of the maxilla was less than uniform. The lack of linear correlation between appliance opening and skeletal expansion is attributable to multiple factors, including those related to the device, the surgical technique, and the craniofacial deformity itself. (Oral Surg Oral Med Oral Pathol Oral Radiol Endod 2008; 106: 812-819)