Synthesis and coordination chemistry of 2-(di-2-pyridylamino)pyrimidine; structural aspects of spin crossover in an Fe(II) complex

This paper was accepted on February 26 20122-(Di-2-pyridylamino)pyrimidine (L), a potentially ditopic tetradentate ligand, was synthesized from commercially available di-2-pyridylamine and 2-chloropyrimidine. Despite being capable of bridging two metal atoms with bidentate chelation of both metal centres, L prefers to chelate or bridge through the more basic pyridyl donors of the di-2-pyridylamine moiety. Mononuclear trans-[Fe(NCS)2(L)2] and [Cu(L)2(H2O)](BF4)2•H2O complexes, and a discrete [Ag2(L)4](PF6)2 metallomacrocycle were isolated and structurally characterized by X-ray crystallography. A mononuclear palladium complex [PdCl2(L)]•(solvate), where solvate = ½H2O or CH2Cl2, was also readily obtained in 71% yield. One example of the ligand acting as a bis(bidentate) bridging ligand was observed in a dinuclear [(PdCl2)2(L)]•¾H2O complex that was obtained only in very low yield (ca. 3%) from the reaction that produced [PdCl2(L)]•½H2O. trans-[Fe(NCS)2(L)2] undergoes a temperature dependent HS-LS (HS = high spin; LS = low spin) crossover at ca. 205 K that was 2 observed by X-ray crystallography and magnetic measurements and attempts were made to understand the structural basis of this process. Despite efforts to isolate examples of L bridging two iron(II) centres, only the mononuclear trans-[Fe(NCS)2(L)2] species could be obtained.Rachel S. Crees, Boujemma Moubaraki, Keith S. Murray, and Christopher J. Sumb

On the possibility of magneto-structural correlations: detailed studies of di-nickel carboxylate complexes

A series of water-bridged dinickel complexes of the general formula [Ni<sub>2</sub>(μ<sub>2</sub>-OH<sub>2</sub>)(μ2- O<sub>2</sub>C<sup>t</sup>Bu)<sub>2</sub>(O<sub>2</sub>C<sup>t</sup>Bu)2(L)(L0)] (L = HO<sub>2</sub>C<sup>t</sup>Bu, L0 = HO<sub>2</sub>C<sup>t</sup>Bu (1), pyridine (2), 3-methylpyridine (4); L = L0 = pyridine (3), 3-methylpyridine (5)) has been synthesized and structurally characterized by X-ray crystallography. The magnetic properties have been probed by magnetometry and EPR spectroscopy, and detailed measurements show that the axial zero-field splitting, D, of the nickel(ii) ions is on the same order as the isotropic exchange interaction, J, between the nickel sites. The isotropic exchange interaction can be related to the angle between the nickel centers and the bridging water molecule, while the magnitude of D can be related to the coordination sphere at the nickel sites

Experimental study of pedestrian flow through a bottleneck

In this work the results of a bottleneck experiment with pedestrians are presented in the form of total times, fluxes, specific fluxes, and time gaps. A main aim was to find the dependence of these values from the bottleneck width. The results show a linear decline of the specific flux with increasing width as long as only one person at a time can pass, and a constant value for larger bottleneck widths. Differences between small (one person at a time) and wide bottlenecks (two persons at a time) were also found in the distribution of time gaps.Comment: accepted for publication in J. Stat. Mec

Biological anthropology in the Indo-Pacific Region: New approaches to age-old questions

Biological anthropological research, the study of both modern and past humans, is a burgeoning field in the Indo-Pacific region. It is becoming increasingly apparent that the unique environments of the Indo-Pacific have resulted in an archaeological record that does not necessarily align with those in the northern hemisphere. New, regionally-specific archaeological models are being developed, and biological anthropological research has an important role to play in establishing past human experience within these models. In the Indo-Pacific, research using ancient and modern human tissues is adding insight into global processes of prehistoric settlement and migrations, subsistence change and human biosocial adaptation. This review synthesises current themes in biological anthropology in this region. It highlights the diverse methods and approaches used by biological anthropologists to address globally-relevant archaeological questions. In recent decades a collaborative approach between archaeologists, biological anthropologists and local communities has become the norm in the region. The many positive outcomes of this multi-disciplinary approach are highlighted here through the use of regionally-specific case studies. This review ultimately aims to stimulate further collaborations between archaeologists, biological anthropologists and the communities in the region, and demonstrate how the evidence from Indo-Pacific research may be relevant to global archaeological models

Derailment-based fault tree analysis on risk management of railway turnout systems

Railway turnouts are fundamental mechanical infrastructures, which allow a rolling stock to divert one direction to another. As those are of a large number of engineering subsystems, e.g. track, signalling, earthworks, these particular sub-systems are expected to induce high potential through various kind of failure mechanisms. This could be a cause of any catastrophic event. A derailment, one of undesirable events in railway operation, often results, albeit rare occurs, in damaging to rolling stock, railway infrastructure and disrupt service, and has the potential to cause casualties and even loss of lives. As a result, it is quite significant that a well-designed risk analysis is performed to create awareness of hazards and to identify what parts of the systems may be at risk. This study will focus on all types of environment based failures as a result of numerous contributing factors noted officially as accident reports. This risk analysis is designed to help industry to minimise the occurrence of accidents at railway turnouts. The methodology of the study relies on accurate assessment of derailment likelihood, and is based on statistical multiple factors-integrated accident rate analysis. The study is prepared in the way of establishing product risks and faults, and showing the impact of potential process by Boolean algebra

Travel to school and housing markets: a case study of Sheffield, England

How children travel to school is at the centre of a complex set of interrelated issues with significant policy implications. This paper reviews the relation of patterns of travel to school to concerns about public health, school choice, urban form, and residential housing markets. The spatial relations between pupils’ homes and the schools that they attend provides the basis of an analytical framework that links local neighbourhood characteristics, school performance, and house prices to the distance and mode of travel to school and the level of ‘excess commuting’ in the urban system. A unique analysis of several integrated micro-datasets from Sheffield, UK, suggests that, while there are high levels of excess commuting, there remains a complex interrelationship between housing and neighbourhood characteristics, school performance, and commuting patterns. There are differences between the pictures for primary schools and secondary schools. Policies aimed at promoting transport efficiency and those promoting school choice are likely to remain in tension

Noncontact ultrasound imaging applied to cortical bone phantoms

Purpose: The purpose of this paper was to take the first steps toward applying noncontact ultrasound (NCU) to the tasks of monitoring osteoporosis and quantitative ultrasound imaging (QUS) of cortical bone. The authors also focused on the advantages of NCU, such as its lack of reliance on a technologist to apply transducers and a layer of acoustical coupling gel, the ability of the transducers to operate autonomously as specified by preprogrammed software, and the likely reduction in statistical and systematic errors associated with the variability in the pressure applied by the clinician to the transmitting transducer that NCU might provide. The authors also undertook this study in order to find additional applications of NCU beyond its past limited usage in assessing the severity of third degree burns. Methods: A noncontact ultrasound imaging system using a pair of specially designed broadband, 1.5 MHz noncontact piezoelectric transducers and cortical bone phantoms, were used to determine bone mineral density (BMD), speed of sound (SOS), integrated response (IR), and ultrasonic transmittance. Air gaps of greater than 3 cm, two transmission and two reflection paths, and a digital signal processor were also used in the collection of data from phantoms of nominal mass densities that varied from 1.17 to 2.25 g/cm3 and in bone mineral density from 0 to 1.7 g/cm3. Results: Good correlations between known BMD and measured SOS, IR, and transmittance were obtained for all 17 phantoms, and methods for quantifying and minimizing sources of systematic errors were outlined. The BMD of the phantom sets extended through most of the in vivo range found in cortical bone. A total of 16–20 repeated measurements of the SOS, thickness, and IR for the phantom set that were conducted over a period of several months showed a small variation in the range of measurements of ±1%–2%. These NCU data were shown to be in agreement with similar results using contact ultrasound to be within 1%–2%. Transmittance images of cortical bone phantoms showed differences in the nominal overall BMD values of the phantoms that were large enough to be distinguished by a visual examination. A list of possible sources of errors in quantitative NCU was also included in this study. Conclusions: The results of this paper suggest that NCU might find additional applications in medical imaging, beyond its original and only previous usage in assessing third degree burns. The fact that the authors’ phantom measurements using conventional, gel coupled ultrasound are in agreement with those obtained with NCU demonstrates that in spite of large additional levels of attenuation of up to 150 dB and new error sources, NCU could have comparable levels of accuracy to those of conventional quantitative ultrasound, while providing the medical and patient comfort-related advantages of not involving direct contact

Rigidification of a macrocyclic tris-catecholate scaffold leads to electronic localisation of its mixed valent redox product

The catecholate groups in [{Pt(L)}3(μ3-tctq)] (H6tctq = 2,3,6,7,10,11-hexahydroxy-4b,8b,12b,12d-tetramethyltribenzotriquinacene; L = a diphosphine chelate) undergo sequential oxidation to their semiquinonate forms by voltammetry, with ΔE½ = 160–170 mV. The monoradical [{Pt(dppb)}3(μ3-tctq•)]+ is valence-localised, with no evidence for intervalence charge transfer in its near-IR spectrum. This contrasts with previously reported [{Pt(dppb)}3(μ3-ctc•)]+ (H6ctc = cyclotricatechylene), based on the same macrocyclic tris-dioxolene scaffold, which exhibits partly delocalised (class II) mixed valency

Tetrahedral intrinsic structure of Oxygen-16 revisited

Abstract: A model for vibrational and rotational excitations of an intrinsic tetrahedral structure of the Oxygen-16 nucleus has been investigated, building on classic work of Wheeler, Dennison and Robson. Tetrahedral A- and F-phonons are treated harmonically, but the E-phonon dynamics is extended to dynamics on an E-manifold of configurations of four α-particles. This allows for tunnelling between the tetrahedral configuration and its dual, through a square configuration, and lifts the parity doubling that would otherwise occur. Unlike in earlier models, including the algebraic cluster model, the E-phonon frequency is taken to be about half the F-phonon frequency, which in turn is about half the A-phonon frequency. As a result, the first-excited 0+ state is a 2-phonon, E-manifold excitation, whereas the lowest 2+ and 2− states are 1-phonon, E-manifold excitations. Coriolis contributions to the rotational energy of states with F-phonons are significant. Altogether, rotational bands are constructed based on vibrational states with up to four phonons, and with spin/parity up to 9−. Nearly all the observed states of Oxygen-16 are accommodated, up to 20 MeV and partly beyond. Predictions for some so far unobserved states, especially those of unnatural parity, are made