Ab-initio calculations of the proton location in topaz-OH, Al2SiO4(OH)2

The position of hydrogen in the structure of topaz-OH was determined by means of ab-initio quantum-mechanic calculations. Static lattice energy calculations predict the existence of four non-equivalent positions of protons, which are characterized by O4-H1... O1, O4-H2... O2, O4-H3... O3 and O4-H4... O4 hydrogen bonds. The distribution of the protons between positions of local equilibrium is controlled by the proton-proton avoidance rule and the strength of the hydrogen bonds. The most favourable configuration of hydrogen atoms is achieved for adjacent protons, which form O4-H3... O3 and O4-H4... O4 hydrogen bonds, respectively. The thermal excitation of atoms at a temperature of 55 K is large enough for the hydrogen atoms occasionally to change their positions to form O4-H1... O1 and O4-H2... O2 bonds. At ambient pressures and higher temperatures the protons are in a dynamic exchange between the allowed positions of local minima. As a consequence, for nearly room-temperature conditions, the dynamic change between different structural configurations leads to the violation of all possible symmetry elements and with that to space group #E5/E5#1. The flipping of the protons between different sites is achieved by simple rotation of the OH-dipole and does not produce any significant distortion of the framework of topaz, whose symmetry remains that of the space group Pbnm. Therefore, no reduction of symmetry has been observed in former X-ray studies on topaz-OH. Calculated IR absorption spectra of topaz-OH were found to be in good agreement with measured spectra. According to the calculations, the two favourable configurations of protons might correspond to the measured peak splitting within the OH-stretching range. An experimentally observed low-frequency band at 3520 cm−1 was assigned to the OH-stretching of the O4-H3... O3 bond, while the band at 3600 cm−1 was attributed to OH-stretching of the O4-H4... O4 hydrogen bond. The broad peak in FAR-IR frequency range at 100-150 cm−1 is attributed to the stretching of H3... O3 and H4... O4 contacts. The rate of proton exchange at 670 K among different sites was estimated by ab-inito molecular dynamic simulations. The calculations predict that flipping of adjacent protons between O4-H3... O3 and O4-H4... O4 bonds at 670 K occur at a rate of about 1.96 TH

The hysteroscopic view of infertility: the mid-secretory endometrium and treatment success towards pregnancy

The purpose of this study was the analysis of a correlation, in infertile patients, between the quality of the endometrium based on its vascularisation and the chances of conception. Hysteroscopy was carried out to determine the quality of the endometrial surface using the Sakumoto-Masamoto classification ("good” vs. "poor” endometrium) in the secretory phase of the menstrual cycle. The results were set in relation to the outcome of the subsequent infertility treatment, i.e. the establishment of a pregnancy within the study period (4years). In 108 (67%) of the 162 followed-up patients, the endometrium was endoscopically classified as "good”, while in 54 (33%) the result was "poor”. The overall pregnancy rate was 37% (60 patients); 47 of all pregnancies (78%) occurred in women with a "good” endometrium while 13 (22%) had a "poor” classification. This positive association between the establishment of a pregnancy in the follow-up and a "good" classification of the endometrial vasculature in the group with a "good" endometrium was significant (P = 0.0165, Fisher's exact test). This study confirms the usefulness of endometrial evaluation by hysteroscopy as a diagnostic instrument for providing a prognosis of the chance for the patients to become pregnan

Spectroscopic and redox properties of amine-unctionalized K_2[Os-^(II)(bpy)(CN)_4] complexes

We report the first examples of amine-functionalized K_2[Os^(II)(bpy)(CN)_4] (bpy = 2,2'-bipyridine) complexes. The tetracyanoosmate complexes were prepared by UV irradiation (λ = 254 nm) of K_4[Os^(II)(CN)_6] and primary amine-functionalized bpy ligands in acidic aqueous media. The aqueous solution pH dependences of the spectroscopic and redox properties of 4,4'- and 5,5'-substituted complexes have been investigated. The pendant amine functional groups and coordinated cyanide ligands are basic sites that can be sequentially protonated, thereby allowing systematic tuning of electrochemical and optical spectroscopic properties

The inter-rater reliability of the diagnosis of surgical site infection in the context of a clinical trial.

ObjectivesThe diagnosis of surgical site infection following endoprosthetic reconstruction for bone tumours is frequently a subjective diagnosis. Large clinical trials use blinded Central Adjudication Committees (CACs) to minimise the variability and bias associated with assessing a clinical outcome. The aim of this study was to determine the level of inter-rater and intra-rater agreement in the diagnosis of surgical site infection in the context of a clinical trial.Materials and methodsThe Prophylactic Antibiotic Regimens in Tumour Surgery (PARITY) trial CAC adjudicated 29 non-PARITY cases of lower extremity endoprosthetic reconstruction. The CAC members classified each case according to the Centers for Disease Control (CDC) criteria for surgical site infection (superficial, deep, or organ space). Combinatorial analysis was used to calculate the smallest CAC panel size required to maximise agreement. A final meeting was held to establish a consensus.ResultsFull or near consensus was reached in 20 of the 29 cases. The Fleiss kappa value was calculated as 0.44 (95% confidence interval (CI) 0.35 to 0.53), or moderate agreement. The greatest statistical agreement was observed in the outcome of no infection, 0.61 (95% CI 0.49 to 0.72, substantial agreement). Panelists reached a full consensus in 12 of 29 cases and near consensus in five of 29 cases when CDC criteria were used (superficial, deep or organ space). A stable maximum Fleiss kappa of 0.46 (95% CI 0.50 to 0.35) at CAC sizes greater than three members was obtained.ConclusionsThere is substantial agreement among the members of the PARITY CAC regarding the presence or absence of surgical site infection. Agreement on the level of infection, however, is more challenging. Additional clinical information routinely collected by the prospective PARITY trial may improve the discriminatory capacity of the CAC in the parent study for the diagnosis of infection.Cite this article: J. Nuttall, N. Evaniew, P. Thornley, A. Griffin, B. Deheshi, T. O'Shea, J. Wunder, P. Ferguson, R. L. Randall, R. Turcotte, P. Schneider, P. McKay, M. Bhandari, M. Ghert. The inter-rater reliability of the diagnosis of surgical site infection in the context of a clinical trial. Bone Joint Res 2016;5:347-352. DOI: 10.1302/2046-3758.58.BJR-2016-0036.R1

A Policy Maker’s Guide to Designing Payments for Ecosystem Services

Over the past five years, there has been increasing interest around the globe in payment schemes for the provision of ecosystem services, such as water purification, carbon sequestration, flood control, etc. Written for an Asian Development Bank project in China, this report provides a user-friendly guide to designing payments for the provision of ecosystem services. Part I explains the different types of ecosystem services, different ways of assessing their value, and why they are traditionally under-protected by law and policy. This is followed by an analysis of when payments for services are a preferable approach to other policy instruments. Part II explains the design issues underlying payments for services. These include identification of the service as well as potential buyers and sellers, the level of service needed, payment timing, payment type, and risk allocation. Part II contains a detailed analysis of the different types of payment mechanisms, ranging from general subsidy and certification to mitigation and offset payments. Part III explores the challenges to designing a payment scheme. These include the ability to monitor service provision, secure property rights, perverse incentives, supporting institutions, and poverty alleviation

The driver landscape of sporadic chordoma.

Chordoma is a malignant, often incurable bone tumour showing notochordal differentiation. Here, we defined the somatic driver landscape of 104 cases of sporadic chordoma. We reveal somatic duplications of the notochordal transcription factor brachyury (T) in up to 27% of cases. These variants recapitulate the rearrangement architecture of the pathogenic germline duplications of T that underlie familial chordoma. In addition, we find potentially clinically actionable PI3K signalling mutations in 16% of cases. Intriguingly, one of the most frequently altered genes, mutated exclusively by inactivating mutation, was LYST (10%), which may represent a novel cancer gene in chordoma.Chordoma is a rare often incurable malignant bone tumour. Here, the authors investigate driver mutations of sporadic chordoma in 104 cases, revealing duplications in notochordal transcription factor brachyury (T), PI3K signalling mutations, and mutations in LYST, a potential novel cancer gene in chordoma

The Period Changes of the Cepheid RT Aurigae

Observations of the light curve for the 3.7-day Cepheid RT Aur both before and since 1980 indicate that the variable is undergoing an overall period increase, amounting to +0.082 +-0.012 s/yr, rather than a period decrease, as implied by all observations prior to 1980. Superposed on the star's O-C variations is a sinusoidal trend that cannot be attributed to random fluctuations in pulsation period. Rather, it appears to arise from light travel time effects in a binary system. The derived orbital period for the system is P = 26,429 +-89 days (72.36 +-0.24 years). The inferred orbital parameters from the O-C residuals differ from those indicated by existing radial velocity data. The latter imply the most reasonable results, namely a1 sin i = 9.09 (+-1.81) x 10^8 km and a minimum secondary mass of M2 = 1.15 +-0.25 Msun. Continued monitoring of the brightness and radial velocity changes in the Cepheid are necessary to confirm the long-term trend and to provide data for a proper spectroscopic solution to the orbit.Comment: Accepted for publication in PASP (November 2007

Movements and Home Ranges of Mountain Plovers Raising Broods in Three Colorado Landscapes

We report movements and home-range sizes of adult Mountain Plovers (Charadrius montanus) with broods on rangeland, agricultural fields, and prairie dog habitats in eastern Colorado. Estimates of home range size (95% fixed kernel) were similar across the three habitats: rangeland (146.1 ha +/- 101.5), agricultural fields (131.6 ha +/- 74.4), and prairie dog towns (243.3 ha +/- 366.3). Our minimum convex polygon estimates of home-range size were comparable to those on rangeland reported by Knopf and Rupert (1996). In addition, movements - defined as the distance between consecutive locations of adults with broods - were equivalent across habitats. However, our findings on prairie dog habitat suggest that home-range size for brood rearing may be related to whether the prairie dog habitat is in a complex of towns or in an isolated town

Movements and Home Ranges of Mountain Plovers Raising Broods in Three Colorado Landscapes

We report movements and home-range sizes of adult Mountain Plovers (Charadrius montanus) with broods on rangeland, agricultural fields, and prairie dog habitats in eastern Colorado. Estimates of home range size (95% fixed kernel) were similar across the three habitats: rangeland (146.1 ha +/- 101.5), agricultural fields (131.6 ha +/- 74.4), and prairie dog towns (243.3 ha +/- 366.3). Our minimum convex polygon estimates of home-range size were comparable to those on rangeland reported by Knopf and Rupert (1996). In addition, movements - defined as the distance between consecutive locations of adults with broods - were equivalent across habitats. However, our findings on prairie dog habitat suggest that home-range size for brood rearing may be related to whether the prairie dog habitat is in a complex of towns or in an isolated town

The driver landscape of sporadic chordoma

Chordoma is a malignant, often incurable bone tumour showing notochordal differentiation. Here, we defined the somatic driver landscape of 104 cases of sporadic chordoma. We reveal somatic duplications of the notochordal transcription factor brachyury (T) in up to 27% of cases. These variants recapitulate the rearrangement architecture of the pathogenic germline duplications of T that underlie familial chordoma. In addition, we find potentially clinically actionable PI3K signalling mutations in 16% of cases. Intriguingly, one of the most frequently altered genes, mutated exclusively by inactivating mutation, was LYST (10%), which may represent a novel cancer gene in chordoma