Imposing high-symmetry and tuneable geometry on lanthanide centres with chelating Pt and Pd metalloligands

Exploitation of HSAB preferences allows for high-yield, one-pot syntheses of lanthanide complexes chelated by two Pd or Pt metalloligands, [MII(SAc)4]2− (SAc− = thioacetate, M = Pd, Pt). The resulting complexes with 8 oxygen donors surrounding the lanthanides can be isolated in crystallographically tetragonal environments as either [NEt4]+ (space group: P4/mcc) or [PPh4]+ (space group: P4/n) salts. In the case of M = Pt, the complete series of lanthanide complexes has been structurally characterized as the [NEt4]+ salts (except for Ln = Pm), while the [PPh4]+ salts have been structurally characterized for Ln = Gd–Er, Y. For M = Pd, selected lanthanide complexes have been structurally characterized as both salts. The only significant structural difference between salts of the two counter ions is the resulting twist angle connecting tetragonal prismatic and tetragonal anti-prismatic configurations, with the [PPh4]+ salts approaching ideal D4d symmetry very closely (φ = 44.52–44.61°) while the [NEt4]+ salts exhibit intermediate twist angles in the interval φ = 17.28–27.41°, the twist increasing as the complete 4f series is traversed. Static magnetic properties for the latter half of the lanthanide series are found to agree well in the high temperature limit with the expected Curie behavior. Perpendicular and parallel mode EPR spectroscopy on randomly oriented powder samples and single crystals of the Gd complexes with respectively Pd- and Pt-based metalloligands demonstrate the nature of the platinum metal to strongly affect the spectra. Consistent parametrization of all of the EPR spectra reveals the main difference to stem from a large difference in the magnitude of the leading axial term, B02, this being almost four times larger for the Pt-based complexes as compared to the Pd analogues, indicating a direct Pt(5dz2)–Ln interaction and an arguable coordination number of 10 rather than 8. The parametrization of the EPR spectra also confirms that off-diagonal operators are associated with non-zero parameters for the [NEt4]+ salts, while only contributing minimally for the [PPh4]+ salts in which lanthanide coordination approximates D4d point group symmetry closely.LHD acknowledges support from NSF-CCT EMT 08-517. (08-517 - NSF-CCT EMT

Visual evoked potentials in children prenatally exposed to methylmercury

Prenatal exposure to methylmercury can cause both neurobehavioral deficits and neurophysiological changes. However, evidence of neurotoxic effects within the visual nervous system is inconsistent, possibly due to incomplete statistical adjustment for beneficial nutritional factors. We evaluated the effect of prenatal methylmercury exposure on visual evoked potential (VEP) latencies in Faroese children with elevated prenatal methylmercury exposure. A cohort of 182 singleton term births was assembled in the Faroe Islands during 1994–1995. At age 7 years, VEP tracings were obtained from 139 cohort subjects after exclusion of subjects with abnormal vision conditions. We used multiple regression analysis to evaluate the association of mercury concentrations in cord blood and maternal hair at parturition with VEP latencies after adjustment for potential confounders that included the cord-serum phospholipid concentration of n-3 polyunsaturated fatty acids (PUFAs) and the duration of breastfeeding. Unadjusted correlations between mercury exposure and VEP latencies were equivocal. Multiple regression models showed that increased mercury concentrations, especially in maternal hair, were associated with delayed latencies for VEP peak N145. After covariate adjustment, a delay of 2.22 ms (p = 0.02) was seen for each doubling of the mercury concentration in maternal hair. In agreement with neuropsychological findings, the present study suggests that prenatal methylmercury exposure may have an adverse effect on VEP findings despite the absence of clinical toxicity to the visual system. However, this association was apparent only after adjustment for n-3 PUFA status

Semen quality and reproductive hormones in Faroese men: a cross-sectional population-based study of 481 men

Objectives To determine semen quality and reproductive hormone levels in young Faroese men. Design Descriptive cross-sectional study of Faroese men compared with Danish men. Setting Faroese one-centre study. Participants 481 men born from 1981 to 1987 and investigated from 2007 to 2010. Outcome measures Sperm concentration, semen volume, total sperm count, sperm motility, sperm morphology and reproductive hormone levels. Results Sperm concentrations for the Faroese men were lower than for the Danish men (crude median 40 vs 48 mill/ml, p<0.0005). Semen volume was higher, and thus the total sperm counts did not differ (159 vs 151 mill, p=0.2). Motility and morphology did not differ between the Faroese and Danes. The inhibin B/follicle-stimulating hormone ratios for the Faroese men were lower than for the Danes (64 vs 76, p=0.001). Similarly, lower total testosterone/luteinising hormone (LH) ratio (4.6 vs 6.0, p<0.0005) and lower calculated free-testosterone/LH ratio (94 vs 134, p<0.0005) were detected for the Faroese men. Conclusions Semen quality among the Faroese men is at the same low level as reported for Danish men, and the reproductive hormone levels furthermore indicated a lower Leydig cell capacity for testosterone production. The influence of environmental exposure and genetic factors on semen quality has to be studied further

Micromechanical fatigue experiments for validation of microstructure-sensitive fatigue simulation models

Crack initiation governs high cycle fatigue life and is sensitive to microstructural details. While corresponding microstructure-sensitive models are available, their validation is difficult. We propose a validation framework where a fatigue test is mimicked in a sub-modeling simulation by embedding the measured microstructure into the specimen geometry and adopting an approximation of the experimental boundary conditions. Exemplary, a phenomenological crystal plasticity model was applied to predict deformation in ferritic steel (EN1.4003). Hotspots in commonly used fatigue indicator parameter maps are compared with damage segmented from micrographs. Along with the data, the framework is published for benchmarking future micromechanical fatigue models

Micromechanical fatigue experiments for validation of microstructure-sensitive fatigue simulation models

Crack initiation governs high cycle fatigue life and is sensitive to microstructural details. While corresponding microstructure-sensitive models are available, their validation is difficult. We propose a validation framework where a fatigue test is mimicked in a sub-modeling simulation by embedding the measured microstructure into the specimen geometry and adopting an approximation of the experimental boundary conditions. Exemplary, a phenomenological crystal plasticity model was applied to predict deformation in ferritic steel (EN1.4003). Hotspots in commonly used fatigue indicator parameter maps are compared with damage segmented from micrographs. Along with the data, the framework is published for benchmarking future micromechanical fatigue models

Differential Response of Bacterial Microdiversity to Simulated Global Change

ACKNOWLEDGMENTS UC Irvine and the LRGCE are located on the ancestral homelands of the Indigenous Kizh and Acjachemen nations. We thank Alejandra Rodriguez Verdugo, Katrine Whiteson, Kendra Walters, Cynthia Rodriguez, Kristin Barbour, Alberto Barron Sandoval, Joanna Wang, Joia Kai Capocchi, Pauline Uyen Phuong Nguyen, Khanh Thuy Huynh, and Clara Barnosky for their input on analyses and previous drafts and for laboratory help. This work was supported by the U.S. Department of Energy, Office of Science, Office of Biological and Environmental Research grants DE-SC0016410 and DE-SC0020382.Peer reviewedPublisher PD

Phase Synchronization in Railway Timetables

Timetable construction belongs to the most important optimization problems in public transport. Finding optimal or near-optimal timetables under the subsidiary conditions of minimizing travel times and other criteria is a targeted contribution to the functioning of public transport. In addition to efficiency (given, e.g., by minimal average travel times), a significant feature of a timetable is its robustness against delay propagation. Here we study the balance of efficiency and robustness in long-distance railway timetables (in particular the current long-distance railway timetable in Germany) from the perspective of synchronization, exploiting the fact that a major part of the trains run nearly periodically. We find that synchronization is highest at intermediate-sized stations. We argue that this synchronization perspective opens a new avenue towards an understanding of railway timetables by representing them as spatio-temporal phase patterns. Robustness and efficiency can then be viewed as properties of this phase pattern

Harmonic generation in ring-shaped molecules

We study numerically the interaction between an intense circularly polarized laser field and an electron moving in a potential which has a discrete cylindrical symmetry with respect to the laser pulse propagation direction. This setup serves as a simple model, e.g., for benzene and other aromatic compounds. From general symmetry considerations, within a Floquet approach, selection rules for the harmonic generation [O. Alon Phys. Rev. Lett. 80 3743 (1998)] have been derived recently. Instead, the results we present in this paper have been obtained solving the time-dependent Schroedinger equation ab initio for realistic pulse shapes. We find a rich structure which is not always dominated by the laser harmonics.Comment: 15 pages including 7 figure