XUV-induced reactions in benzene on sub-10 fs timescale: nonadiabatic relaxation and proton migration.

Unraveling ultrafast dynamical processes in highly excited molecular species has an impact on our understanding of chemical processes such as combustion or the chemical composition of molecular clouds in the universe. In this article we use short (<7 fs) XUV pulses to produce excited cationic states of benzene molecules and probe their dynamics using few-cycle VIS/NIR laser pulses. The excited states produced by the XUV pulses lie in an especially complex spectral region where multi-electronic effects play a dominant role. We show that very fast τ ≈ 20 fs nonadiabatic processes dominate the relaxation of these states, in agreement with the timescale expected for most excited cationic states in benzene. In the CH3+ fragmentation channel of the doubly ionized benzene cation we identify pathways that involve structural rearrangement and proton migration to a specific carbon atom. Further, we observe non-trivial transient behavior in this fragment channel, which can be interpreted either in terms of propagation of the nuclear wavepacket in the initially excited electronic state of the cation or as a two-step electronic relaxation via an intermediate state.

XUV excitation followed by ultrafast non-adiabatic relaxation in PAH molecules as a femto-astrochemistry experiment.

Highly excited molecular species are at play in the chemistry of interstellar media and are involved in the creation of radiation damage in a biological tissue. Recently developed ultrashort extreme ultraviolet light sources offer the high excitation energies and ultrafast time-resolution required for probing the dynamics of highly excited molecular states on femtosecond (fs) (1 fs=10(-15) s) and even attosecond (as) (1 as=10(-18) s) timescales. Here we show that polycyclic aromatic hydrocarbons (PAHs) undergo ultrafast relaxation on a few tens of femtoseconds timescales, involving an interplay between the electronic and vibrational degrees of freedom. Our work reveals a general property of excited radical PAHs that can help to elucidate the assignment of diffuse interstellar absorption bands in astrochemistry, and provides a benchmark for the manner in which coupled electronic and nuclear dynamics determines reaction pathways in large molecules following extreme ultraviolet excitation.

Alignment dependent enhancement of the photoelectron cutoff for multiphoton ionization of molecules.

The multiphoton ionization rate of molecules depends on the alignment of the molecular axis with respect to the ionizing laser polarization. By studying molecular frame photoelectron angular distributions from N(2), O(2), and benzene, we illustrate how the angle-dependent ionization rate affects the photoelectron cutoff energy. We find alignment can enhance the high energy cutoff of the photoelectron spectrum when probing along a nodal plane or when ionization is otherwise suppressed. This is supported by calculations using a tunneling model with a single ion state.

Measurement and control of plasma oscillations in femtosecond filaments.

The short-lived longitudinal plasma oscillations generated during filamentation in argon and nitrogen gas are measured with a specially designed current monitor. The magnitude and initial direction of the corresponding currents depend sensitively on laser polarization and nature of the gas. The results are interpreted as resulting from the competition between two forces acting on free electrons born during the filamentation process: the Lorentz laser force and a Coulomb wake force resulting from a lateral expansion of the plasma.

Precise in-situ measurement of laser pulse intensity using strong field ionization.

Building on the work of Alnaser et al. [Phys. Rev. A 70, 023413 (2004)], we devise an improved method for an in-situ measurement of the peak intensity in a focused, femtosecond infrared laser pulse. The method is shown to be effective with both photoion and photoelectron imaging devices. The model used to fit the experimental data has no unphysical free parameters used in fitting. The accuracy of the fit is 4% and the overall accuracy of the measurement is 8%.

Partitioning of the linear photon momentum in multiphoton ionization.

The balance of the linear photon momentum in multiphoton ionization is studied experimentally. In the experiment argon and neon atoms are singly ionized by circularly polarized laser pulses with a wavelength of 800 and 1400 nm in the intensity range of 10(14)-10(15) W/cm2. The photoelectrons are measured using velocity map imaging. We find that the photoelectrons carry linear momentum corresponding to the photons absorbed above the field free ionization threshold. Our finding has implications for concurrent models of the generation of terahertz radiation in filaments.

Direct test of laser tunneling with electron momentum imaging.

Tunneling is often used to describe multiphoton ionization of rare gas atoms in infrared fields. We test the tunneling approximation and its nonadiabatic extension by measuring the unperturbed momentum distribution along the κ direction of a circularly polarized light pulse. We find substantial, but not total, agreement between our results and the predictions of the model. As predicted, the κ direction momentum distribution is Gaussian and its width increases with the square root of electric field strength. However, the width is 15% too large and we find no evidence of nonadiabatic effects as we approach the expected limits of the approximation.

Bioaccumulation of persistent organic pollutants in female common dolphins (Delphinus delphis) and harbour porpoises (Phocoena phocoena) from western European seas: geographical trends, causal factors and effects on reproduction and mortality.

Concentrations of polychlorinated biphenyls (PCBs) in blubber of female common dolphins and harbour porpoises from the Atlantic coast of Europe were frequently above the threshold at which effects on reproduction could be expected, in 40% and 47% of cases respectively. This rose to 74% for porpoises from the southern North Sea. PCB concentrations were also high in southern North Sea fish. The average pregnancy rate recorded in porpoises (42%) in the study area was lower than in the western Atlantic but that in common dolphins (25%) was similar to that of the western Atlantic population. Porpoises that died from disease or parasitic infection had higher concentrations of persistent organic pollutants (POPs) than animals dying from other causes. Few of the common dolphins sampled had died from disease or parasitic infection. POP profiles in common dolphin blubber were related to individual feeding history while those in porpoises were more strongly related to condition.

Cell cycle-dependent phosphorylation of the ATRX protein correlates with changes in nuclear matrix and chromatin association.

Mutations in the ATRX gene are associated with an X-linked mental retardation (XLMR) syndrome most often accompanied by alpha-thalassaemia (ATR-X syndrome). The ATRX gene encodes a predicted protein of 280 kDa featuring a PHD zinc finger motif and an ATPase/helicase domain of the SWI/SNF type; the vast majority of mutations in the ATRX gene fall within these two motifs. Although these domains are suggestive of a role for ATRX in transcriptional regulation by affecting chromatin structure and/or function, the precise cellular role of the ATRX protein remains undefined. Using indirect immunofluorescence and biochemical fractionation, we demonstrate that the ATRX protein has a punctate nuclear staining pattern and that it is tightly associated with the nuclear matrix at interphase. At the onset of M phase, the ATRX protein was associated mainly with condensed chromatin. The association of the ATRX protein with chromosomes at mitosis is concomitant with phosphorylation of the protein and its association with heterochromatin protein 1alpha (HP1alpha). The phosphorylation-dependent changes in localization between the nuclear matrix and condensed chromatin are consistent with a dual role for ATRX, possibly involving gene regulation at interphase and chromosomal segregation at mitosis.

Postmortem investigations on winter stranded sperm whales from the coasts of Belgium and The Netherlands.

During winter 1994-95, four and three sperm whales (Physeter macrocephalus) were stranded along the Belgian and the Dutch coasts, respectively. Necropsies and tissue samplings were collected 24 hrs post mortem. Lesions on several whales included round and linear skin scars, ventral skin abrasions, acute skin ulcers, acute ulcerative stomatitides, acute to chronic external otitides, and passive visceral congestion. In addition, these sperm whales appeared to be debilitated with severe weight deficit, had blubber thickness reduction, the absence of abdominal fat, and the intestinal tracts were almost empty. Three categories of lesions and their possible relation with the stranding were evaluated. Cutaneous scars observed on the seven whales appeared to have no relation with the stranding. The poor body condition and acute integument ulcerative lesions were present before the stranding. Ventral skin abrasions and visceral passive congestion were caused by the strandings. Absence of food in the alimentary tracts, evidence of weight loss and blubber thickness reduction were compatible with an extended presence of the sperm whales in the North Sea, where adequate food is not available. This might lead to progressive weakness, predisposing the animals to secondary pathogens such as viral diseases. Finally, the coastal configuration of the southern North Sea makes it a trap for sperm whales which have entered the area during their wanderings.

Mutations in the hemagglutinin and matrix genes of a virulent influenza virus variant, A/FM/1/47-MA, control different stages in pathogenesis.

The mouse adapted strain of influenza A/FM/1/47 virus, FM-MA, has increased virulence due to mutations in HA, M1 and at least one other, unmapped, genome segment. Genetic reassortants that differ due to the HA or M1 mutations were used to define the role of these mutations in pathogenesis. Pathological changes in lungs of infected mice were assessed by hematoxylin phloxine saffron (HPS) staining, and viral infection was measured by fluorescent antibody staining of thin sections and flow cytometry of lung parenchymal cells. HA played a role in bronchiolar pathology by increasing necrosis of bronchiolar epithelium, peribronchiolar lymphocytes, and airway obstruction. The HA mutation was shown to be responsible for a 0.2 unit decreased in the pH optimum of fusion and controlled resistance to alpha and beta inhibitors of hemagglutination. Both these changes in biology may confer a replicative advantage in bronchioles seen in the first day of infection. Thus the HA mutation may have conferred a survival advantage in the extracellular lung environment. The M1 mutation resulted in improved growth in the lung and cultured cells and was associated with increases in recruitment of macrophages, spread of infection into the alveoli of the lung and interstitial pneumonia. Sequence analysis indicated that the unmapped mutation in the control of FM-MA virulence is either the K482-->R substitution in the PB2 protein or the D538-->G substitution in the PB1 protein. One or other of these mutations results in a growth advantage in infected lung but not in cultured cells as well as a further increased recruitment and infection of macrophages in the lung. Infection with virulent strains of influenza that induced increases in macrophage recruitment caused hypothermia in the mouse.

Polychlorinated Biphenyls, Dibenzo-p-dioxins, and Dibenzofurans in Harbor Porpoises (Phocoena phocoena) Stranded on the Dutch Coast Between 1990 and 1993

Congener-specific polychlorinated biphenyl (PCB) concentrations were determined in the blubber, kidney, and liver tissues of 22 harbor porpoises (Phocoena phocoena) stranded on the Dutch coast. For comparison, the PCB concentrations in blubber and liver samples of four porpoises from the vicinity of Greenland were investigated. In ten blubber samples, the non-ortho PCB concentrations were determined, while in four of these the levels of chlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were analyzed. It is shown that the PCB level increases with age in males, whereas in mature females the levels remain relatively constant. A comparison with earlier data indicates a slight decrease over the last 20 years in the PCB burden of porpoises living near the Dutch coast. The amount of the most prominent and persistent congener, PCB 153, can be related to the feeding pattern of male porpoises; it appears to be completely retained in this species. Bioaccumulation of non-ortho PCBs and PCDD/Fs does not take place. The overall toxicity, expressed as 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQ), is mostly covered by di-ortho and mono-ortho PCBs, depending on age and sex, whereas the contribution of the notorious toxic PCDDs and PCDFs to the overall TEQ is at most 0.5%.

The influenza virus variant A/FM/1/47-MA possesses single amino acid replacements in the hemagglutinin, controlling virulence, and in the matrix protein, controlling virulence as well as growth.

Genetic analysis of mouse-adapted influenza virus variant A/FM/1/47 (FM) MA has previously identified four genome segments, 4, 5, 7, and 8, that are statistically associated with virulence. On sequencing these genome segments, we found single amino acid replacements at amino acid 47 of the HA2 subunit of the hemagglutinin and at amino acid 139 of the matrix protein. Mutation was not detected in segments 5 and 8, obviating a role for these genes in FM-MA virulence. FM-MA replicates to higher titer than FM in MDCK cells and in mouse lung. FM X FM-MA reassortants were used to show that the M1 gene controlled replication in MDCK cells as well as in mouse lung.

[The position of seals in the system of mammals (author's transl)]. / De plaats van de zeehonde in het systeem der zoogdieren.

The common seal Phoca vitulina belongs to the order Pinnipedia, a group of marine mammals, the majority of which live in the colder seas. Two main groups are differentiated within this order: Otarioidea and Phocoidea. The Otarioidea are divided into two families: Otariidae (sea lions and fur seals) and Odobenidae (walruses): the Phocoidea consist of the family Phocidae (seals) only. The Pinnipedia are closely related to the order Carnivora: they probably originated about 50 million years ago from a group of mammals related to bears. Otarioidea and Phocoidea are now usually regarded as close relatives, n view of among others, biochemical and parasitological characters.