Personality traits and endocrine response as possible asymmetry factors of agonistic outcome in karate athletes.

Individual variations of plasma levels of hormones testosterone (T) and cortisol (C), before (pre) and after (post) Kumite (real fight) and Kata (ritualized fight) were measured in male karate athletes and analyzed in relation with the agonistic outcome (i.e. winning or losing the fight) and personality trait measures. T and C increased only during Kumite contest and pre- and post-competition C levels were higher in losers than winners. Losers showed higher levels of harm avoidance and anxiety as well as lower level of novelty seeking than winners. Importantly, novelty seeking negatively correlates with pre C and the higher the level of risk assessment, emotionality and insecurity indexes the higher the pre C level. In conclusion, personality traits might be an important factor asymmetry between athletes influencing both the probability of winning or losing an agonistic interaction and the different anticipatory endocrine response to the incipient fight.

Molecular structures of M(Bu(t))3 (M = Al, Ga, In) using gas-phase electron diffraction and ab initio calculations: experimental and computational evidence for charge-transfer processes leading to photodissociation.

The gas-phase structures of AI(Bu')3 and Ga(Bu')3 have been investigated by electron diffraction and are shown to consist of monomeric units with very slightly pyramidal geometries. Salient structural parameters (r(hl)) include r(A1-C) = 2.008(2) A and r(Ga-C) = 2.032(2) A. For both compounds the ligand orientations and geometries are controlled by interligand interactions. The structures of M(Bu(t))3 (M = Al, Ga, In) have been calculated ab initio and those for the aluminium and gallium derivatives are in good agreement with the electron-diffraction structures. Comparison of the ab initio calculated structure of In(Bu')3 with those of Al(Bu(t))3 and Ga(Bu(t))3 suggests that the significantly different photochemistry exhibited by the former does not result from structural factors. In fact the compounds undergo a charge-transfer process in the UV region, with the wavelength required calculated to be slightly longer for the indium compound than for the other two.

Effects of oil pollution at Kuwait's greater Al-Burgan oil field on polycyclic aromatic hydrocarbon concentrations in the tissues of the desert lizard Acanthodactylus scutellatus and their ant prey.

Using indicator species to monitor the effects of oil pollution was thought to be useful to assess whether local desert reptiles and their insect prey could fulfill such a role in an area damaged in the second Gulf War (1990). Polluted sites with apparently different degrees of contamination (namely tar mat, soot, and clear sites) located at Kuwait's Greater Al-Burgan oil field were compared with control areas outside this region in study conducted in 2002. Five Acanthodactylus scutellatus lizards from each study and control site were humanely killed and stored in a freezer at -20 degrees C until analysis. Ants from the same sites were also collected and treated in a similar manner. Lizard and ant whole body tissues were subjected to gas chromatography-mass spectrometry (GC-MS) to determine concentrations of petroleum hydrocarbons (HCs). The study concentrated on sixteen polycyclic aromatic hydrocarbons (PAHs), EPA priority pollutants used as indicators of petrogenic HC contamination. There were significantly different concentrations of total PAHs in lizards and ants among all four study sites. Of the 16 PAHs, phenanthrene, fluoranthene, and benzo[a]anthracene were present in both lizard and ant samples from the Greater Al-Burgan oil field sites irrespective of the apparent degree of pollution but were undetectable in materials from the control sites. The range of total PAHs in lizards was 26.5-301 ng g(-1) and it was 6.7-82.1 ng g(-1) in ants. Concentrations increased progressively along an expected contamination gradient. Total PAHs were detected in biota even in an area (clear site) that did not appear, virtually, to contain petroleum soil pollution which supports the value of indicator biota species. For all three sites where PAHs were found in biota, the ratio of total PAHs in ants to lizards was consistently 3.3-3.4. These data show that, although 12 years have passed since the Kuwait oil spill catastrophe, all sites are still contaminated with PAHs. Use of lizard and ant materials in monitoring such desert locations seems to be an effective strategy.

Accurate equilibrium structures obtained from gas-phase electron diffraction data: sodium chloride.

A novel method has been developed to allow the accurate determination of equilibrium gas-phase structures from experimental data, thus allowing direct comparison with theory. This new method is illustrated through the example of sodium chloride vapor at 943 K. Using this approach the equilibrium structures of the monomer (NaCl) and the dimer (Na(2)Cl(2)), together with the fraction of vapor existing as dimer, have been determined by gas-phase electron diffraction supplemented with data from microwave spectroscopy and ab initio calculations. Root-mean-square amplitudes of vibration (u) and distance corrections (r(a) - r(e)) have been calculated explicitly from the ab initio potential-energy surfaces corresponding to the vibrational modes of the monomer and dimer. These u and (r(a) - r(e)) values essentially include all of the effects associated with large-amplitude modes of vibration and anharmonicity; using them we have been able to relate the ra distances from a gas-phase electron diffraction experiment directly to the re distances from ab initio calculations. Vibrational amplitudes and distance corrections are compared with those obtained by previous methods using both purely harmonic force fields and those including cubic anharmonic contributions, and the differences are discussed. The gas-phase equilibrium structural parameters are r(e)(Na-Cl)(monomer) = 236.0794(4) pm; r(e)(Na-Cl)(dimer) = 253.4(9) pm; and <(e)ClNaCl = 102.7(11) degrees. These results are found to be in good agreement with high-level ab initio calculations and are substantially more precise than those obtained in previous structural studies.

The molecular structure of N-fluorobis(trifluoromethanesulfonyl)imide, NF(SO(2)CF(3))(2), as studied in the gas phase by electron diffraction restrained by ab initio calculations.

The structure of N-fluorobis(trifluoromethylsulfonyl)imide, prepared by a relatively safe and easy method, has been determined by gas-phase electron diffraction (GED), employing the SARACEN method, with flexible restraints based on the MP2/6-311G* structure, and by X-ray crystallography at 150 K. The strongly electron-withdrawing CF(3) and SO(2)CF(3) groups make the C-S and N-S distances long, averaging 187.7(3) and 171.7(3) pm, respectively, in the gas phase. The gas consists of two conformers, one (75%) with a CF(3) group on each side of the SNS plane, one anti-periplanar and one syn-periplanar to the further N-S bond (ap, sp), and the other with both CF(3) groups on the same side, i.e. denoted ap, ap. These conformers have very different SNS angles, 126.9(9) degrees and 117.1(17) degrees respectively. In the crystal all molecules have the ap, sp conformation, with parameters similar to those found for this conformer in the gas phase.

Social stress, coping strategies and tumor development in male mice: behavioral, neuroendocrine and immunological implications.

The relationships between acute social stress, immunological alterations and the development of pulmonary metastases of B16F10 melanoma were analyzed. In particular, the effects of different behavioral coping strategies on the development of the metastases were studied. Tumor bearing and tumor non-bearing mice were subjected for 24h to a sensory contact social stress model. This included two 5 min sessions of direct social interaction with their resident cagemates (which had been selected for consistent levels of aggression). The subjects' behavior was videotaped and assessed. Corticosterone, IL-2, IL-12 and splenic cell proliferation responses to Con-A were determined 1h and 3 days post-stress. Lung metastatic foci numbers were determined 21 days after inoculation (15 days post-stress). Social stress increased the number of pulmonary metastases and the serum level of corticosterone but decreased the splenic proliferative capacity. No direct relationship could be established between the development of the metastases and the assayed interleukin response. A combination of cluster and discriminant analyses established that there were three types of coping strategies. Subjects engaging in a strategy characterized by an absence of attack, low non-social exploration levels and high levels of defense, subordination and avoidance, developed most pulmonary metastases. Social stress effects on tumor development appear to depend on the subject's coping strategy in such situations (although one cannot rule out the possibility that differences in the development of the disease per se are responsible for the different behavioral patterns observed).

Dietary fats influence 'open-field' behaviour of male and female laboratory mice.

Swiss mice of differing ages (juvenile and adult) and sexes were fed four specially formulated, pelleted diets containing respectively 8% saturated vegetable fat, 8% soya oil, 8% olive oil and 2% soya oil (with identities hidden from the experimenter) or a local commercial chow (3% crude fat) for 3 or 6 weeks. Subjects were individually housed and were assessed under red lighting for behaviour in a modified 'open field' (a 30 x 20 cm box with a black floor). Videotaped records were analysed using 'The Observer' system, quantifying transitions between inner and outer zones, rearing, freezing, grooming and defaecation as well as location in the two equal-sized zones. Clearly, these non-isocaloric diets differed in palatability, producing complex effects on growth as well as physiological and behavioural measures. Many indices were influenced by age, sex, and the duration of dietary exposure. Interactions between factors were common. Defaecation does not seem to provide a useful index of 'emotionality' in this type of study and investigations lacking a wide range of indices seem unlikely to provide unequivocal support for postulated links between dietary lipids and behaviour. The study broadly supports the contention that dietary fats subtly influence mood in mice.

Gas-phase structure of (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(eta(2)-1,5-cyclooctadiene)copper(I), Cu(1,5-cod)(hfac), an important precursor for vapor deposition of copper.

The molecular structure of Cu(1,5-cod)(hfac) in the gas phase has been determined by electron diffraction, restrained by parameters calculated ab initio (MP2/AE1 level) or using Density Functional Theory (BP86/AE1 level). The most stable structure is one in which one olefinic group of the cyclooctadiene ligand is coordinated to the square-planar copper atom [refined Cu-C distances 194.0(13) and 194.4(9) pm]. The second C=C double bond is weakly associated with the copper atom [Cu...C distances 267.2(23) and 276.9(25) pm], and the cyclooctadiene ligand has a twist-boat conformation, so that the complex has C(1) symmetry. The nature of the bonding between copper and each of the two olefin moieties has been assessed by topological analysis of the BP86/AE1 total electron density. A form with C(2) symmetry, lying between 2 and 7 kJ mol(-1) above the ground state, is a transition state for exchange of the two olefinic groups. There are also two higher energy conformers, both 10 kJ mol(-1) or more above the ground state. In one of these the cyclooctadiene ligand retains the twist-boat conformation, but the Cu(hfac) moiety is coordinated in the exo position with respect to the noncoordinated olefin, instead of endo, as in the most stable conformer. The molecular symmetry is C(1) in this isomer. In the remaining form the ligand has the chair conformation, and the molecular symmetry is C(s).

A specific anti-aggressive effect of repeatedly administered lobeline.

The effects of chronic treatments with nicotinic agonists on agonistic encounters have received little attention. The effects of repeated (for 10 days) SC administration of (-)-lobeline (9.3, 18.6 and 37.2 micromol/kg) and (-)-nicotine (0.93, 1.86 and 3.72 micromol/kg) were evaluated using the mouse isolation-induced aggression model. Individually housed OF1 male mice served as experimental animals and were confronted by 'standard opponents'. Each mouse was tested only once on the last day of the repeated drug treatment. Videotaped agonistic encounters were analysed estimating the times allocated to 11 behavioural categories. Repeated treatment with the highest dose of lobeline diminished attack behaviour without significantly increasing immobility or changing any other behavioural category involving motor activity. In contrast, nicotine did not significantly alter time allocated to any behavioural category.

Effect of low doses of clozapine on behaviour of isolated and group-housed male mice in the elevated plus-maze test.

Clozapine is effective over a low and narrow dose range in the treatment of the negative symptoms of schizophrenia. Its efficacy is said to reflect an anxiolytic property of the neuroleptic. This study examined the effects of a low dose range of clozapine (0.1, 0.2 and 0.4 mg/kg) administered to isolated (7 days) and group-housed male mice on their behaviour in the elevated plus-maze. The results using this model of anxiety showed no dose-dependent effect on behaviour after treatment with low doses of clozapine. Some doses (0.1 and 0.4 mg/kg), however, reduced the duration and frequency of open arm entries compared to control-treated mice in the group-housed animals. This might indicate a slight anxiogenic effect. Support for this view is provided by some of the ethological measures, particularly head-dipping (HD). Seven days of isolation did not alter the main anxiety indices in controls. Nevertheless, some measures (e.g. closed entries and duration in the closed arm) were modified by the clozapine treatment (0.2 mg/kg) in a manner suggesting a mild anxiogenic action. The effects of the drug in individually and group-housed male mice were certainly different.

Sex and death: CHD1Z associated with high mortality in moorhens.

Sex ratios in clutches of moorhens (Gallinula chloropus) in Britain were measured on 83 chicks using the sex-linked CHD1 gene (Chromo-helicase/ATPase-DNA binding protein 1). Among birds, the female is the heterogametic sex (Z and W chromosomes), and the male is homogametic (two copies of the Z chromosome). We report variation among the PCR-amplified fragments of the CHD1Z, and the death of nearly all heterozygous male chicks (92%). In contrast, survivorship among females and homozygote males was 54-60%. Mortality in male heterozygotes was significantly higher than that of male homozygotes (P < 0.001). Chick and egg biometrics were not significantly different between these males. The CHD1Z was unlikely to be directly responsible but may have been hitchhiked by the causal gene(s). The observations appear to follow a classic underdominance (heterozygote inferiority) pattern, but raise the paradoxical question of why one form of the Z chromosome has not been fixed, as is expected from evolutionary theory. We discuss possible explanations and include a survey of British populations based on skin specimens.

Gas-Phase Reaction of Tetraborane(10) and Ethyne: Molecular Structure of nido-1,2-C(2)B(3)H(7) in the Gas Phase.

The molecular structure of nido-1,2-C(2)B(3)H(7), 1, the principal volatile carborane generated in the quenched gas-phase reaction of B(4)H(10) and ethyne at 70 degrees C, has been determined by a combined analysis of gas-phase electron-diffraction data and rotation constants restrained by ab initio computations at the CCSD(T)/TZP' level. The structure is consistent with a geometry having C(s)() symmetry, similar to that of pentaborane(9). The apical position is occupied by a carbon atom, displaced toward B(4) from a position directly above the B(5).B(3) vector, and hydrogen atoms asymmetrically bridge the B-B bonds. The basal atoms are almost coplanar, C(2) lying ca. 2 degrees below the B(3)-B(4)-B(5) plane. Important experimental structural parameters (r(alpha) degrees /pm, angle(alpha)/ degrees ) are r[C(1)-C(2)] = 162.6(6); r[C(1)-B(3)] = 161.4(3); r[C(2)-B(3)] = 154.3(2); r[C(1)-B(4)] = 157.4(5); r[B(3)-B(4)] = 185.7(3);

Molecular Structure of Chlorodifluoronitrosomethane, CClF(2)NO, As Determined in the Gas Phase by Electron Diffraction and ab Initio Calculations.

The gas-phase structure of chlorodifluoronitrosomethane, CClF(2)NO, has been determined by electron diffraction and calculated ab initio. Theoretically, CClF(2)NO is predicted to consist of two conformers having C(s)() (phi = 0 degrees ) and C(1) (phi = 105 degrees ) symmetry, which are near degenerate in energy, DeltaE = 1.1 kJ mol(-1) [TZ2P/MP2 + ZPE(DZP/MP2)], and separated by a barrier of around 1 kJ mol(-1). Equivalent C(1) conformers are predicted to be connected by a barrier of around 5-10 kJ mol(-1). The low predicted barriers to interconversion of the two conformers suggest that the rotation of the nitroso group can be regarded as being barely restricted over most values of the torsional angle at room temperature. This conclusion is supported by the gas-phase electron diffraction data, for which a dynamic model employing 11 conformations was needed to obtain an accurate fit to the experimental data. The final refined values of structural parameters for the two conformers (C(s)()/C(1)) are (r(alpha)/pm,<(alpha)/deg) as follows: C(1)-N(2) 156.7(5)/155.9(5), N(2)-O(3) 117.5(3)/117.9(3), C(1)-Cl(4) 173.9(2)/174.2(2), C(1)-F 132.0(2)/132.1(2) and 131.0(2), C(1)-N(2)-O(3) 110.8(12)/110.7(12), N(2)-C(1)-Cl(4) 117.5(5)/108.9(5), N(2)-C(1)-F 103.7(2)/104.2(2) and 111.6(2), Cl(4)-C(1)-N(2)-F 123.6(14)/119.2(14) and 123.7(14).

Differences Between Gas-Phase and Solid-State Molecular Structures of the Simplest Phosphonium Ylide, Me3 P=CH2.

Clearly different from local C3 symmetric is the heavy-atom core of Me3 P=CH2 , the simplest phosphonium ylide. The geometry obtained by reanalysis of gas-electron-diffraction data from 1977 is now consistent with theoretical calculations, but different from the molecular structure in the solid state. The picture shows the structure of Me3 P=CH2 in the gas phase (a) and in the crystal (c) together with the calculated transition state (b) (viewed along the P=C bond).

Molecular Structure of 3,4-Dimethylenehexa-1,5-diene ([4]Dendralene), C(8)H(10), in the Gas Phase As Determined by Electron Diffraction and ab Initio Calculations.

The molecular structure of 3,4-dimethylenehexa-1,5-diene ([4]dendralene), C(8)H(10), has been determined in the gas phase. A single conformer with C(2) symmetry, having two almost planar, anti butadiene groups orientated with a dihedral angle C(2)C(3)C(4)C(5) of 71.7(19) degrees, is detected by electron diffraction employing flexible restraints derived from ab initio computations. Other experimental structural parameters (r(alpha)/pm, angle(alpha)/ degrees ) are: C(1)=C(2) 133.4(1), C(3)=C(7) (not in main chain) 134.0(1), C(2)-C(3) 147.4(2), C(3)-C(4) 149.6(3), C(1)C(2)C(3) 124.4(3), C(2)C(3)C(4) 119.2(5), C(4)C(3)C(7) 117.6(7), and C(7)C(3)C(2)C(1) -174.8(28). Ab initio computations at the MP2/6-311G level predict that the vapor consists of ca. 90% of the conformer found experimentally, the other 10% comprising four other conformers.

Molecular Structure of Trifluorophosphine Tetraborane(8), B(4)H(8)PF(3), As Determined in the Gas Phase by Electron Diffraction and ab Initio Computations.

The molecular structure of trifluorophosphine tetraborane(8), B(4)H(8)PF(3), has been studied in the gas phase by electron diffraction. The experimental data can be fitted using a model which represents the gas as consisting solely of the endo conformer with C(s)() symmetry, the PF(3) group staggered with respect to the B(1)-H(1) bond. Important experimental structural parameters (r(alpha) degrees ) are r[B(1)-B(2)] (hinge-wing) = 184.7(9) pm, r[B(1)-B(3)] (hinge-hinge) = 172.2(12) pm, r[B(2)-B(3)] = 179.9(10) pm,r[B(1)-P] = 179.8(9) pm, and r(P-F) (mean) = 152.8(1) pm; B(3)B(1)P = 131.6(11) degrees, and the dihedral ("butterfly") angle between the planes B(1)B(2)B(3) and B(1)B(4)B(3) is 133.9(23) degrees. These values agree well with the ab initio (MP2/TZP level) optimized molecular geometry for the endo conformer; at the MP2/TZP//MP2/TZP + ZPE(HF/6-31G) level, the exo conformer is predicted to represent ca. 2% of the compound vapor, consistent with the experimental (11)B NMR solution spectrum. The experimental and theoretical geometries are supported by comparison of the calculated (IGLO) (11)B NMR chemical shifts with the experimental NMR data.

Molecular Structures of Methyldifluoroarsine, CH(3)AsF(2), and Dimethylfluoroarsine, (CH(3))(2)AsF, in the Gas Phase As Determined by Electron Diffraction and ab InitioCalculations.

The structures of gaseous CH(3)AsF(2) and (CH(3))(2)AsF have been determined by electron diffraction incorporating vibrational amplitudes derived from ab initio force fields scaled by experimental frequencies and, for the difluoride, restrained by microwave constants. The following parameters (r(alpha) degrees structure, distances in pm, angles in degrees) have been determined for CH(3)AsF(2): r(As-C) = 194.6(4), r(As-F) = 173.1(1), angleCAsF = 95.2(1), angleFAsF = 97.0(1). For (CH(3))(2)AsF structural refinement gives r(As-C) = 195.1(1), r(As-F) = 175.4(1), angleCAsF = 95.3(5), and angleCAsC = 96.9(8). For the series (CH(3))(3)As, (CH(3))(2)AsF, CH(3)AsF(2), and AsF(3), both As-C and As-F bond lengths are shortened with increasing numbers of F atoms, but the angles CAsF and FAsF are almost invariant.

1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C(2)B(10)H(11). Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations.

The compound 1-phenyl-1,2-dicarba-closo-dodecaborane(12), 1-C(6)H(5)-1,2-closo-C(2)B(10)H(11) (1), has been synthesized and characterized by a complete assignment of its (11)B NMR spectrum via (11)B{(1)H}/(11)B{(1)H} (COSY), (1)H{(11)B(selective)} and (1)H{(11)B}/(1)H{(11)B} (COSY) spectroscopy. An electron- and X-ray diffraction investigation of 1, complemented by ab initio calculations, has been undertaken. The gas-phase electron-diffraction (GED) data can be fitted by several models describing conformations which differ in the position of the phenyl ring with respect to the carborane cage. Local symmetries ofC(2)(v)() and D(6)(h)() for the 1,2-C(2)B(10) and C(6) moieties, respectively, were adopted in the GED model in order to simplify the problem. In addition, constraints among the close-lying C-C and B-B bonds were employed. However, even though such simplifications led to satisfactory refinements (R(G) = 0.069-0.071), a unique, definitive solution could not be gained. The (C-C)(mean), (C-B)(mean) and (B-B)(mean) bond lengths,r(a), are ca. 1.44, 1.72, and 1.78 Å, respectively. The C(6) hexagon, with r(a)(C-C) = ca. 1.394 Å, either eclipses the C(1)-C(2) vector (overall C(s)() symmetry) or more or less eclipses the C(1)-B(4) cluster bond (overall C(1) symmetry). In contrast, in the solid at 199 K, the ring lies at a position intermediate between the two GED positions, as determined by X-ray crystallography [C(8)H(16)B(10), monoclinic P2(1)/a: a = 12.047(3) Å, b = 18.627(4) Å, c = 12.332(5) Å, beta = 110.09(4) degrees, Z = 8]. The C-B distances span the range 1.681(6)-1.743(5) Å, and B-B lengths lie between 1.756(6) and 1.795(6) Å. A similar conformation was found for the theoretical (RHF/6-31G level) structure which was fully optimized in C(1) symmetry. The r(e) distances are consistent with the dimensions derived in the experimental studies. IGLO calculations of the (11)B chemical shifts, in addition to SCF single-point energies of the GED structures, further support these observations.