Molecular Freedom of the Ammonium Ion. Heat Capacity and Thermodynamic Properties of Ammonium Perchlorate from 5°–350°K

The heat capacity of NH4ClO4 has been determined by adiabatic calorimetry from 5°–350°K and found to be of simple sigmate character without thermal anomalies. The heat capacity (Cp)(Cp), entropy (S°)(S°), enthalpy function (H°−H°0) / T(H°−H°0)∕T, and Gibbs energy function (G°−G0°) / T(G°−G0°)∕T evaluated at 298.15°K from these data are 30.61, 44.02, 20.24, and −23.78 cal/(gfm °K). Combination of these values with aqueous NH4ClO4 thermochemical data suggests the absence of zero‐point entropy. Comparison with the heat capacity of isostructural KClO4 permits resolution of the molecular dynamics of the ammonium ions and leads to the conclusion that these ions are restricted rotators, prevented from freely rotating by comparatively low‐energy barriers.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/70216/2/JCPSA6-50-12-5083-1.pd

Optical spectra and thermal Schottky levels in dysprosium sesquisulfide

We report a detailed crystal-field splitting analysis of the energy levels of Dy3+(4f9)Dy3+(4f9) in single crystals of Dy2S3Dy2S3 that have the Th3P4Th3P4 cubic defect structure. From an analysis of the temperature-dependent absorption spectra, we have identified seven of the eight crystal-field split energy (Stark) levels of the ground-state multiplet manifold, 6H15/2.6H15/2. Sixty-two experimental Stark levels from various multiplet manifolds of Dy3+Dy3+ are compared with a calculated crystal-field splitting, whose initial crystal-field parameters, Bnm,Bnm, were determined from lattice-sum calculations. The rms deviation between experimental and calculated levels is 7 cm−1. Both the experimental and calculated crystal-field splitting of the 6H15/26H15/2 manifold are compared with an assignment of Schottky levels obtained from a reassessment of heat capacity data reported earlier. Based on entropy considerations and verification of the Schottky level assignments by analyses of the optical and magnetic susceptibility data, we conclude that the anomaly observed in the heat capacity data near 3.4 K is due to antiferromagnetic ordering. © 1999 American Institute of Physics.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/69677/2/JCPSA6-110-24-12125-1.pd

Thermophysical Properties of CeB 6 and PrB 6 at Subambient Temperatures

Equilibrium adiabatic heat-capacity measurements have been made on zone refined samples of CeB 6 and PrB 6 . Companion measurements made on LaB 6 , NdB 6 , and GdB 6 have been reported elsewhere. These show cooperative lambda-type anomalies associated with antiferro-magnetic ordering. Except for lanthanum hexaboride, Schottky internal crystal field levels result in significant contributions to the thermodynamic functions. The gross thermodynamic properties at 298.15 K heat capacity ( C p / R ), entropy increment (Δ 0,m T S 0 / R ), and Gibbs energy function are correlated with the nature of the lanthanide. For LaB 6 , CeB 6 , PrB 6 , NdB 6 , and GdB 6 the three properties are, respectively: {11.654, 12.014, 11.997, 11.916, 11.695} C p / R ; {10.001, 11.803, 12.430, 12.558, 13.982} S 0 /R, and finally {4.379, 5.912, 6.232, 6.451, 7.905} Φ m 0 / R .Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/43146/1/10973_2004_Article_5116049.pd

Modeling Sub- and Super-ambient Heat Capacities of the Group Iva Compounds Despite the Lanthanide Contraction

This paper is concerned with the estimation of heat capacities in the IVA 3d-transition element compounds using especially Zr and Hf compounds as examples. Most prediction schemes routinely tacitly assume that volumes and masses trend ‘in parallel’. However, the lanthanide contraction here ensures for ZrX/HfX systems — and generally elsewhere — that this is not so in this portion of the periodic table. Available methods such as Latimer's, Volumetric Priority, Komada-Westrum, Grimvall's, and Sommers' are compared on IVA elements and compounds. Only the Sommers approach has volumetric input. It provides the best prediction.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/43144/1/10973_2004_Article_250156.pd

The type and frequency of interactions that occur between staff and children outside in Early Years Foundation Stage settings during a fixed playtime period when there are tricycles available

This study reports on an investigation into adult and child interactions observed in the outdoor play environment in four Local Authority early years foundation stage settings in England. In this instance the common two features across the settings were the presence of tricycles and a timetabled outdoor play period. In total, across the four schools, there were 204 children. The study aimed to gain an understanding of the nature of the dialogues between staff and children, that is, the types of exchange that occurred when either the child approached an adult or the adult approached a child. The most frequent type of utterance was also analysed. The study concludes that adults in these settings spoke more than children and the greatest type of utterance was that of the adult about domestic matters. When the child initiated the conversation there were more extended child utterances than domestic utterances. This may suggest that children wish to be involved in conversations of depth and meaning and that staff need to become aware of how to develop this conversational language with children

Influences on uptake of reproductive health services in Nsangi community of Uganda and their implications for cervical cancer screening

<p>Abstract</p> <p>Background</p> <p>Cervical cancer is the most common female cancer in Uganda. Over 80% of women diagnosed or referred with cervical cancer in Mulago national referral and teaching hospital have advanced disease. Plans are underway for systematic screening programmes based on visual inspection, as Pap smear screening is not feasible for this low resource country. Effectiveness of population screening programmes requires high uptake and for cervical cancer, minimal loss to follow up. Uganda has poor indicators of reproductive health (RH) services uptake; 10% postnatal care attendance, 23% contraceptive prevalence, and 38% skilled attendance at delivery. For antenatal attendance, attendance to one visit is 90%, but less than 50% for completion of care, i.e. three or more visits.</p> <p>Methods</p> <p>We conducted a qualitative study using eight focus group discussions with a total of 82 participants (16 men, 46 women and 20 health workers). We aimed to better understand factors that influence usage of available reproductive health care services and how they would relate to cervical cancer screening, as well as identify feasible interventions to improve cervical cancer screening uptake.</p> <p>Results</p> <p>Barriers identified after framework analysis included ignorance about cervical cancer, cultural constructs/beliefs about the illness, economic factors, domestic gender power relations, alternative authoritative sources of reproductive health knowledge, and unfriendly health care services. We discuss how these findings may inform future planned screening programmes in the Ugandan context.</p> <p>Conclusion</p> <p>Knowledge about cervical cancer among Ugandan women is very low. For an effective cervical cancer-screening programme, awareness about cervical cancer needs to be increased. Health planners need to note the power of the various authoritative sources of reproductive health knowledge such as paternal aunts (<it>Sengas</it>) and involve them in the awareness campaign. Cultural and economic issues dictate the perceived reluctance by men to participate in women's reproductive health issues; men in this community are, however, potential willing partners if appropriately informed. Health planners should address the loss of confidence in current health care units, as well as consider use of other cervical cancer screening delivery systems such as mobile clinics/camps.</p

Quality of dietary fat and genetic risk of type 2 diabetes: individual participant data meta-analysis.

OBJECTIVE: To investigate whether the genetic burden of type 2 diabetes modifies the association between the quality of dietary fat and the incidence of type 2 diabetes. DESIGN: Individual participant data meta-analysis. DATA SOURCES: Eligible prospective cohort studies were systematically sourced from studies published between January 1970 and February 2017 through electronic searches in major medical databases (Medline, Embase, and Scopus) and discussion with investigators. REVIEW METHODS: Data from cohort studies or multicohort consortia with available genome-wide genetic data and information about the quality of dietary fat and the incidence of type 2 diabetes in participants of European descent was sought. Prospective cohorts that had accrued five or more years of follow-up were included. The type 2 diabetes genetic risk profile was characterized by a 68-variant polygenic risk score weighted by published effect sizes. Diet was recorded by using validated cohort-specific dietary assessment tools. Outcome measures were summary adjusted hazard ratios of incident type 2 diabetes for polygenic risk score, isocaloric replacement of carbohydrate (refined starch and sugars) with types of fat, and the interaction of types of fat with polygenic risk score. RESULTS: Of 102 305 participants from 15 prospective cohort studies, 20 015 type 2 diabetes cases were documented after a median follow-up of 12 years (interquartile range 9.4-14.2). The hazard ratio of type 2 diabetes per increment of 10 risk alleles in the polygenic risk score was 1.64 (95% confidence interval 1.54 to 1.75, I2=7.1%, τ2=0.003). The increase of polyunsaturated fat and total omega 6 polyunsaturated fat intake in place of carbohydrate was associated with a lower risk of type 2 diabetes, with hazard ratios of 0.90 (0.82 to 0.98, I2=18.0%, τ2=0.006; per 5% of energy) and 0.99 (0.97 to 1.00, I2=58.8%, τ2=0.001; per increment of 1 g/d), respectively. Increasing monounsaturated fat in place of carbohydrate was associated with a higher risk of type 2 diabetes (hazard ratio 1.10, 95% confidence interval 1.01 to 1.19, I2=25.9%, τ2=0.006; per 5% of energy). Evidence of small study effects was detected for the overall association of polyunsaturated fat with the risk of type 2 diabetes, but not for the omega 6 polyunsaturated fat and monounsaturated fat associations. Significant interactions between dietary fat and polygenic risk score on the risk of type 2 diabetes (P>0.05 for interaction) were not observed. CONCLUSIONS: These data indicate that genetic burden and the quality of dietary fat are each associated with the incidence of type 2 diabetes. The findings do not support tailoring recommendations on the quality of dietary fat to individual type 2 diabetes genetic risk profiles for the primary prevention of type 2 diabetes, and suggest that dietary fat is associated with the risk of type 2 diabetes across the spectrum of type 2 diabetes genetic risk.The EPIC-InterAct study received funding from the European Union (Integrated Project LSHM-CT-2006-037197 in the Framework Programme 6 of the European Community). We thank all EPIC participants and staff for their contribution to the study. We thank Nicola Kerrison (MRC Epidemiology Unit, University of Cambridge, Cambridge, UK) for managing the data for the InterAct Project. In addition, InterAct investigators acknowledge funding from the following agencies: MT: Health Research Fund (FIS) of the Spanish Ministry of Health; the CIBER en Epidemiología y Salud Pública (CIBERESP), Spain; Murcia Regional Government (N° 6236); JS: JS was supported by a Heisenberg-Professorship (SP716/2-1), a Clinical Research Group (KFO218/1) and a research group (Molecular Nutrition to JS) of the Bundesministerium für Bildung und Forschung (BMBF); YTvdS, JWJB, PHP, IS: Verification of diabetes cases was additionally funded by NL Agency grant IGE05012 and an Incentive Grant from the Board of the UMC Utrecht; HBBdM: Dutch Ministry of Public Health, Welfare and Sports (VWS), Netherlands Cancer Registry (NKR), LK Research Funds, Dutch Prevention Funds, Dutch ZON (Zorg Onderzoek Nederland), World Cancer Research Fund (WCRF), Statistics Netherlands (The Netherlands); MDCL: Health Research Fund (FIS) of the Spanish Ministry of Health; Murcia Regional Government (N° 6236); FLC: Cancer Research UK; PD: Wellcome Trust; LG: Swedish Research Council; GH: The county of Västerbotten; RK: Deutsche Krebshilfe; TJK: Cancer Research UK; KK: Medical Research Council UK, Cancer Research UK; AK: Medical Research Council (Cambridge Lipidomics Biomarker Research Initiative); CN: Health Research Fund (FIS) of the Spanish Ministry of Health; Murcia Regional Government (N° 6236); KO: Danish Cancer Society; OP: Faculty of Health Science, 47 University of Aarhus, Denmark; JRQ: Asturias Regional Government; LRS: Asturias Regional Government; AT: Danish Cancer Society; RT: AIRE-ONLUS Ragusa, AVIS-Ragusa, Sicilian Regional Government; DLvdA, WMMV: Dutch Ministry of Public Health, Welfare and Sports (VWS), Netherlands Cancer Registry (NKR), LK Research Funds, Dutch Prevention Funds, Dutch ZON (Zorg Onderzoek Nederland), World Cancer Research Fund (WCRF), Statistics Netherlands (The Netherlands); MMC: Wellcome Trust (083270/Z/07/Z), MRC (G0601261)

Discovery and fine-mapping of adiposity loci using high density imputation of genome-wide association studies in individuals of African ancestry: African Ancestry Anthropometry Genetics Consortium

Genome-wide association studies (GWAS) have identified >300 loci associated with measures of adiposity including body mass index (BMI) and waist-to-hip ratio (adjusted for BMI, WHRadjBMI), but few have been identified through screening of the African ancestry genomes. We performed large scale meta-analyses and replications in up to 52,895 individuals for BMI and up to 23,095 individuals for WHRadjBMI from the African Ancestry Anthropometry Genetics Consortium (AAAGC) using 1000 Genomes phase 1 imputed GWAS to improve coverage of both common and low frequency variants in the low linkage disequilibrium African ancestry genomes. In the sex-combined analyses, we identified one novel locus (TCF7L2/HABP2) for WHRadjBMI and eight previously established loci at P < 5×10−8: seven for BMI, and one for WHRadjBMI in African ancestry individuals. An additional novel locus (SPRYD7/DLEU2) was identified for WHRadjBMI when combined with European GWAS. In the sex-stratified analyses, we identified three novel loci for BMI (INTS10/LPL and MLC1 in men, IRX4/IRX2 in women) and four for WHRadjBMI (SSX2IP, CASC8, PDE3B and ZDHHC1/HSD11B2 in women) in individuals of African ancestry or both African and European ancestry. For four of the novel variants, the minor allele frequency was low (<5%). In the trans-ethnic fine mapping of 47 BMI loci and 27 WHRadjBMI loci that were locus-wide significant (P < 0.05 adjusted for effective number of variants per locus) from the African ancestry sex-combined and sex-stratified analyses, 26 BMI loci and 17 WHRadjBMI loci contained ≤ 20 variants in the credible sets that jointly account for 99% posterior probability of driving the associations. The lead variants in 13 of these loci had a high probability of being causal. As compared to our previous HapMap imputed GWAS for BMI and WHRadjBMI including up to 71,412 and 27,350 African ancestry individuals, respectively, our results suggest that 1000 Genomes imputation showed modest improvement in identifying GWAS loci including low frequency variants. Trans-ethnic meta-analyses further improved fine mapping of putative causal variants in loci shared between the African and European ancestry populations

Genetic Studies of Leptin Concentrations Implicate Leptin in the Regulation of Early Adiposity.

Leptin influences food intake by informing the brain about the status of body fat stores. Rare LEP mutations associated with congenital leptin deficiency cause severe early-onset obesity that can be mitigated by administering leptin. However, the role of genetic regulation of leptin in polygenic obesity remains poorly understood. We performed an exome-based analysis in up to 57,232 individuals of diverse ancestries to identify genetic variants that influence adiposity-adjusted leptin concentrations. We identify five novel variants, including four missense variants, in LEP, ZNF800, KLHL31, and ACTL9, and one intergenic variant near KLF14. The missense variant Val94Met (rs17151919) in LEP was common in individuals of African ancestry only, and its association with lower leptin concentrations was specific to this ancestry (P = 2 × 10-16, n = 3,901). Using in vitro analyses, we show that the Met94 allele decreases leptin secretion. We also show that the Met94 allele is associated with higher BMI in young African-ancestry children but not in adults, suggesting that leptin regulates early adiposity

A multi-disciplinary perspective on emergent and future innovations in peer review [version 2; referees: 2 approved]

Peer review of research articles is a core part of our scholarly communication system. In spite of its importance, the status and purpose of peer review is often contested. What is its role in our modern digital research and communications infrastructure? Does it perform to the high standards with which it is generally regarded? Studies of peer review have shown that it is prone to bias and abuse in numerous dimensions, frequently unreliable, and can fail to detect even fraudulent research. With the advent of web technologies, we are now witnessing a phase of innovation and experimentation in our approaches to peer review. These developments prompted us to examine emerging models of peer review from a range of disciplines and venues, and to ask how they might address some of the issues with our current systems of peer review. We examine the functionality of a range of social Web platforms, and compare these with the traits underlying a viable peer review system: quality control, quantified performance metrics as engagement incentives, and certification and reputation. Ideally, any new systems will demonstrate that they out-perform and reduce the biases of existing models as much as possible. We conclude that there is considerable scope for new peer review initiatives to be developed, each with their own potential issues and advantages. We also propose a novel hybrid platform model that could, at least partially, resolve many of the socio-technical issues associated with peer review, and potentially disrupt the entire scholarly communication system. Success for any such development relies on reaching a critical threshold of research community engagement with both the process and the platform, and therefore cannot be achieved without a significant change of incentives in research environments