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

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

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

Babes, bones, and isotopes: a stable isotope investigation on non-adults from Aventicum, Roman Switzerland (1st-3rd c. CE)

The study of infant feeding practices in archaeological populations can aid in the understanding of cultural attitudes towards dietary choices and how specific circumstances experienced by mothers and their offspring influence childhood health and survivorship. Breastfeeding and weaning patterns have received increased interest in Roman bioarchaeology, especially through the application of stable isotopic investigation of nitrogen (δ15N) and carbon (δ13C) values. This study presents the stable isotopic results of the first Roman bone sample analyzed from Switzerland (30 non-adults and 9 females), allowing us an unprecedented insight into health and diet at the site of Aventicum/Avenches, the capital city of the territory of Helvetii in Roman times (1st-3rd c. AD). The fact that the majority of the non-adult samples subject to stable isotope analysis were perinates, highlights the complex relationship between their δ15N and δ13C values and those of adult females, as different factors, including variation of fetal and maternal stable isotope values, the possible effects of intrauterine growth, as well as maternal/fetal disease and/or nutritional stress (e.g. nutritional deficiencies such as scurvy, parasitic infections, such as malaria), could have influenced the observed elevated δ15N values

Relying on markets to address human rights: sanitation supply chain analysis in low-density settings

Market-based approaches to improving sanitation coverage have increased in recent years, however the equity implications of these approaches, particularly in the face of the recently established human right to sanitation in 2010, requires a closer examination of the costs of sanitation products and services in remote, rural locations. This paper presents results from a recent study examining the sanitation supply-chain in the province of Dien Bien in north-west Vietnam, a low-density rural setting with high rates of poverty. It was found that current toilet coverage is lower in areas of high poverty, and that these areas also experience the highest costs of sanitation products due to the impact of distance and transport costs. We conclude that market-based approaches require nuanced application and that other forms of support or significant market intervention are likely required to ensure equitable outcomes in remote rural contexts

ERK and p38MAPK combine to improve survival in patients with BRAF mutant colorectal cancer

Background In colorectal cancer (CRC), BRAF mutations influence tumour progression. In mismatch repair-deficient (dMMR) tumours, BRAF mutations are associated with a good prognosis, whereas in MMR-competent tumours, they are detrimental. The differential expression of the downstream MAPK pathway members, which are constitutively activated in BRAF mutant patients, may account for these differences. Methods Phosphorylation of ERK, p38MAPK and JNK was assessed by immunohistochemistry, utilising CRC tissue microarrays. A discovery cohort (n = 187) and a validation cohort (n = 801) were analysed for associations with BRAF mutations, clinicopathological characteristics and cancer-specific survival (CSS). Results In 801 CRC patients, nuclear ERK phosphorylation (HR 0.65 95% CI 0.48–0.88, p = 0.004) and the combined nuclear pERK/p-p38 score (HR 0.61 95% CI 0.45–0.82, p = 0.001) were independently associated with CSS, and were further associated with increased BRAF mutations (p = 0.003 and p = 0.002). When stratified for BRAF status, only MMR-competent patients harbouring the mutation and a strong combined nuclear pERK/p-p38 score (HR 0.49 95% CI 0.27–0.89, p = 0.016) demonstrated improved CSS. This improvement in CSS was specific to stage III CRC (HR 0.25 95% CI 0.10–0.64, p = 0.002). Conclusions MMR-competent stage III tumours harbouring BRAF mutations have an improved prognosis when strong nuclear phosphorylation of both ERK and p38MAPK is present

Detection of temporospatially localized growth in ancient Southeast Asia using human skeletal remains

Measures of population growth can provide significant insights into the health, adaptivity and resilience of ancient communities, particularly the way in which human populations respond to major changes, such as the transition to agriculture. To date, paleodemographic tools have facilitated the evaluation of long term, regional population growth, while identification of intraregional variability and short-term growth has been more challenging. This study reports on the application of a new method for estimating the rate of natural population increase (RNPI) from skeletal remains. We have applied the method to ancient Southeast Asian samples and, based on the LOESS fitting procedure, our preliminary results indicate a trend of temporal homogeneity and spatial heterogeneity. This trend is validated against the existing archaeological narrative for the region and, we argue, may indicate intraregional variability in population responses to major technological, economic and sociocultural events, consistent with the variable response observed at the regional level. Due to the critical importance of temporospatial specificity to a vast array of paleodemographic research questions, we have evaluated the precision, assumptions and limitations of this method in the context of other existing paleodemographic methods. Our RNPI measure, in isolation or in combination with existing methods, provides a promising tool that can be used to develop a deeper and more localized understanding of the conditions impacting on population dynamics and, conversely, community responses to change.This research was supported by an Australian Government Research Training Program (RTP) Scholarship and Australian Research Council Grant: FT120100299