Synthesis, Characterization, and Molecular Structure of Bis(tetraphenylcyclopentdienyl)rhodium(II)⊗

A 5 day diglyme reflux of Rh(acac)3 and K(C5HPh4), followed by treatment with aqueous HPF6, produces orange-yellow [(C5HPh4)2Rh]PF66 in 40 - 50% yield. Reduction of [(C5HPh4)2Rh]PF6 with sodium amalgam in THF yields olive green (C5HPh4)2Rh in 70% yield. (C5HPh4)2Rh crystallizes in the triclinic [Error : unloaded OLE object or mail attachment]space group with unit-cell parameters of a = 8.622 (3) Å, b = 10.778 (4) Å, c = 12.894 (5) Å, a = 65.58 (3)°, b = 72.66 (3)°, g = 83.52 (3)°, and Z = 1. The least squares data refined to RF = 7.63% and RwF = 10.12% for the 2479 independent observed reflections with Fo \u3e 5s(Fo ). The metal-centroid distance is 1.904 Å and all other bond lengths and angles are similar to known octaphenylmetallocenes. ESR spectra of (C5HPh4)2Rh in low-temperature glasses display a rhombic g-tensor with resolution of Rh hyperfine splitting on one-g-component. Analysis of the spectral parameters is consistent with a d7 configuration derived from a nearly degenerate dxz, dyz ground state. Voltammetry and coulometry establish the electron-transfer series (C5HPh4)2Rh1+/0/1- with E° values of -1.44 V and -2.13 V vs ferrocene. The heterogeneous charge transfer rate of the second reduction is about three orders of magnitude lower than that of the first

Women\u27s preferences for selective estrogen reuptake modulators: an investigation using the time trade off technique

PurposeSelective Estrogen Receptor Modulators (SERMs) reduce the risk of breast cancer for women at increased risk by 38%. However, uptake is extremely low and the reasons for this are not completely understood. The aims of this study were to utilize time trade-off methods to determine the degree of risk reduction required to make taking SERMs worthwhile to women, and the factors associated with requiring greater risk reduction to take SERMs. MethodsWomen at increased risk of breast cancer (N = 107) were recruited from two familial cancer clinics in Australia. Participants completed a questionnaire either online or in pen and paper format. Hierarchical multiple linear regression analysis was used to analyze the data. ResultsOverall, there was considerable heterogeneity in the degree of risk reduction required to make taking SERMs worthwhile. Women with higher perceived breast cancer risk and those with stronger intentions to undergo (or who had undergone) an oophorectomy required a smaller degree of risk reduction to consider taking SERMs worthwhile. ConclusionWomen at increased familial risk appear motivated to consider SERMs for prevention. A tailored approach to communicating about medical prevention is essential. Health professionals could usefully highlight the absolute (rather than relative) probability of side effects and take into account an individual’s perceived (rather than objective) risk of breast cancer

Immune sensing of Candida albicans requires cooperative recognition of mannans and glucans by lectin and Toll-like receptors

Peer reviewedPublisher PD

New insight to the characteristics and clinical course of clusters of patients with imaging confirmed disc-related sciatica.

BACKGROUND: Referral to secondary care is common for a considerable proportion of patients with persistent sciatica symptoms. It is unclear if information from clinical assessment can further identify distinct subgroups of disc-related sciatica, with perhaps different clinical courses. AIMS: This study aims to identify and describe clusters of imaging confirmed disc-related sciatica patients using latent class analysis, and compare their clinical course. METHODS: The study population were 466 patients with disc-related sciatica. Variables from clinical assessment were included in the analysis. Characteristics of the identified clusters were described and their clinical course over two years, was compared. RESULTS: A four cluster solution was optimal. Cluster 1 (n=110) had mild back and leg pain; cluster 2 (n=59) had moderate back and leg pain, cluster 3 (n=158) had mild back pain and severe leg pain; cluster 4 (n=139) had severe back and leg pain. Patients in cluster 4 had the most severe profile in terms of disability, distress and comorbidity and the lowest reported global change and the smallest proportion of patients with a successful outcome at two years. Of the 135 patients who underwent surgery, 42% and 41% were in clusters 3 and 4 respectively. CONCLUSIONS: Using a strict diagnosis of sciatica, this work identified four clusters of patients primarily differentiated by back and leg pain severity. Patients with severe back and leg pain had the most severe profile at baseline and follow-up irrespective of intervention. This simple classification system may be useful when considering prognosis and management with sciatica patients. This article is protected by copyright. All rights reserved

A Plan for a Long-Term, Automated, Broadband Seismic Monitoring Network on the Global Seafloor

Establishing an extensive and highly durable, long‐term, seafloor network of autonomous broadband seismic stations to complement the land‐based Global Seismographic Network has been a goal of seismologists for decades. Seismic signals, chiefly the vibrations from earthquakes but also signals generated by storms and other environmental processes, have been processed from land‐based seismic stations to build intriguing but incomplete images of the Earth’s interior. Seismologists have mapped structures such as tectonic plates and other crustal remnants sinking deep into the mantle to obtain information on their chemical composition and physical state; but resolution of these structures from land stations is not globally uniform. Because the global surface is two‐thirds ocean, increasing the number of seismic stations located in the oceans is critical for better resolution of the Earth’s interior and tectonic structures. A recommendation for a long‐term seafloor seismic station pilot experiment is presented here. The overarching instrumentation goal of a pilot experiment is performance that will lead to the installation of a large number of long‐term autonomous ocean‐bottom seismic stations. The payoff of a network of stations separated from one another by a few hundred kilometers under the global oceans would be greatly refined resolution of the Earth’s interior at all depths. A second prime result would be enriched understanding of large‐earthquake rupture processes in both oceanic and continental plates. The experiment would take advantage of newly available technologies such as robotic wave gliders that put an affordable autonomous prototype within reach. These technologies would allow data to be relayed to satellites from seismometers that are deployed on the seafloor with long‐lasting, rechargeable batteries. Two regions are presented as promising arenas for such a prototype seafloor seismic station. One site is the central North Atlantic Ocean, and the other high‐interest locale is the central South Pacific Ocean

Transplant Surgery Pipeline: A Report from the American Society of Transplant Surgeons Pipeline Taskforce

BACKGROUND: Transplant surgery fellowship has evolved over the years and today there are 66 accredited training programs in the US and Canada. There is growing concern, however, about the number of US-trained general surgery residents pursuing transplant surgery. In this study, we examined the transplant surgery pipeline, comparing it with other surgical subspecialty fellowships, and characterized the resident transplantation experience. METHODS: Datasets were compiled and analyzed from surgical fellowship match data obtained from the National Resident Matching Program and ACGME reports and relative fellowship competitiveness was assessed. The surgical resident training experience in transplantation was evaluated. RESULTS: From 2006 to 2018, a total of 1,094 applicants have applied for 946 transplant surgery fellowship positions; 299 (27.3%) were US graduates. During this period, there was a 0.8% decrease per year in US-trained surgical residents matching into transplant surgery (p = 0.042). In addition, transplant surgery was one of the least competitive fellowships compared with other National Resident Matching Program surgical subspeciality fellowships, as measured by the number of US applicants per available fellowship position, average number of fellowship programs listed on each applicant\u27s rank list, and proportion of unfilled fellowship positions (each, p \u3c 0.05). Finally, from 2015 to 2017, there were 57 general surgery residency programs that produced 77 transplant surgery fellows, but nearly one-half of the fellows (n = 36 [46.8%]) came from 16 (28.1%) programs. CONCLUSIONS: Transplant surgery is one of the least competitive and sought after surgical fellowships for US-trained residents. These findings highlight the need for dedicated efforts to increase exposure, mentorship, and interest in transplantation to recruit strong US graduates

CO2 enrichment and soil type additively regulate grassland productivity

The development of a predictive understanding of how atmospheric CO2 enrichment is affecting the primary productivity of the terrestrial biosphere is among the most pressing of ecological challenges. The terrestrial biosphere absorbs c. 25% of anthropogenic carbon (C) emissions (Le Quere et al., 2018). Uncertainty in CO2 effects on ecosystem C uptake is a major constraint in the prediction of C cycling and the provisioning of productivity- related ecosystem services. Grasslands cover c. 25% of the terrestrial area and are an important contributor to the global C balance (Sala et al., 1996). CO2 enrichment stimulates the aboveground net primary productivity (ANPP) of most water-limited grasslands by increasing plant water use efficiency (WUE; productivity per unit of transpiration; Morgan et al., 2004; Nowak et al., 2004; Fatichi et al., 2016), but grassland ANPP, as other ecosystem functions, is determined by drivers in addition to water availability which act simultaneously and often interactively with CO2 (Polley et al., 2011). CO2 enrichment usually shows greater stimulation of plant productivity when nitrogen (N) availability is relatively high (Owensby et al., 1994; Reich & Hobbie, 2013; Mueller et al., 2016), for example. Other drivers include precipitation timing (Hovenden et al., 2014), disturbance regimes (Newton et al., 2014), plant species composition (Langley & Megonigal, 2010; Fay et al., 2012; Polley et al., 2012) and soil properties (Epstein et al., 1997, 1998), including soil texture, which influences water availability to plants (Tor-Ngern et al., 2017)

CO2 enrichment and soil type additively regulate grassland productivity

The development of a predictive understanding of how atmospheric CO2 enrichment is affecting the primary productivity of the terrestrial biosphere is among the most pressing of ecological challenges. The terrestrial biosphere absorbs c. 25% of anthropogenic carbon (C) emissions (Le Quere et al., 2018). Uncertainty in CO2 effects on ecosystem C uptake is a major constraint in the prediction of C cycling and the provisioning of productivity- related ecosystem services. Grasslands cover c. 25% of the terrestrial area and are an important contributor to the global C balance (Sala et al., 1996). CO2 enrichment stimulates the aboveground net primary productivity (ANPP) of most water-limited grasslands by increasing plant water use efficiency (WUE; productivity per unit of transpiration; Morgan et al., 2004; Nowak et al., 2004; Fatichi et al., 2016), but grassland ANPP, as other ecosystem functions, is determined by drivers in addition to water availability which act simultaneously and often interactively with CO2 (Polley et al., 2011). CO2 enrichment usually shows greater stimulation of plant productivity when nitrogen (N) availability is relatively high (Owensby et al., 1994; Reich & Hobbie, 2013; Mueller et al., 2016), for example. Other drivers include precipitation timing (Hovenden et al., 2014), disturbance regimes (Newton et al., 2014), plant species composition (Langley & Megonigal, 2010; Fay et al., 2012; Polley et al., 2012) and soil properties (Epstein et al., 1997, 1998), including soil texture, which influences water availability to plants (Tor-Ngern et al., 2017)