(2,2′-Bipyridine-4,4′-dicarb­oxy­lic acid-κ2 N,N′)chlorido(2,2′:6′,2′′-terpyridyl-κ3 N,N′,N′′)ruthenium(II) perchlorate ethanol monosolvate monohydrate

In the title compound, [RuCl(C15H11N3)(C12H8N2O4)]ClO4·C2H5OH·H2O, the geometry of the ClN5 coordination set around the RuII atom is close to octa­hedral, but distorted on account of the limited bite angles of the polypyridyl ligands. The complexes are linked by O—H⋯O hydrogen bonds between the carboxyl groups and the crystal lattice water mol­ecules into chains along [110]. Face-to-face stacking inter­actions are formed between terpyridine ligands, with inter­planar separations of 3.66 (1) and 3.42 (1) Å, and between bipyridine-4,4′-dicarb­oxy­lic acid ligands, with inter­planar separations of 3.65 (1) and 3.72 (1) Å. Three O atoms of the perchlorate ion are each disordered equally over two positions. The hy­droxy group of the ethanol mol­ecule is also disordered over two sites with refined occupancies of 0.794 (9) and 0.206 (9)

Barrierless slow dissociation of photogenerated charge pairs in high-performance polymer-fullerene solar cells

The work in St Andrews was supported by the Engineering and Physical Sciences Research Council (grants EP/L017008/1, EP/J009016/1 and EP/G03673X/1) and the European Research Council (grant 321305). The work in Vilnius was supported by the Research Council of Lithuania (project MIP-85/2015). I.D.W.S. acknowledges support from a Royal Society Wolfson Research Merit Award. D.A.V. is grateful to Supergen SuperSolar Hub for the travel grant. The research data supporting this publication can be accessed at http://dx.doi.org/10.17630/7ec84b4b-d2ab-493c-aaf6-5503a44c0eb5Broadband transient absorption spectroscopy is combined with ultrafast carrier drift measurements to study dissociation of photogenerated charge pairs in efficient photovoltaic blends of the electron donating polymer PTB7 with the acceptor PC71BM. A high ensemble-average mobility sum of electrons and holes is observed which is independent of applied electric field above 12 V/μm and indicates nearly barrier-less pair dissociation at room temperature on a picosecond time scale. High efficiency of pair dissociation in this material is achieved by a combination of high electron mobility in fullerene clusters and hole delocalization along the polymer chain which increases by 30% during dissociation. Our results suggest a predominantly diffusive charge pair dissociation mechanism which requires persistent mobility of both carriers and preferably some delocalization of at least one of them.PostprintPostprintPeer reviewe

Comment on “Discovery of davemaoite, CaSiO₃-perovskite, as a mineral from the lower mantle”

Tschauner et al. (Reports, 11 November 2021, p. 891) present evidence that diamond GRR-1507 formed in the lower mantle. Instead, the data support a much shallower origin in cold, subcratonic lithospheric mantle. X-ray diffraction data are well matched to phases common in microinclusion-bearing lithospheric diamonds. The calculated bulk inclusion composition is too imprecise to uniquely confirm CaSiO₃ stoichiometry and is equally consistent with inclusions observed in other lithospheric diamonds

Hole delocalization as a driving force for charge pair dissociation in organic photovoltaics

This work was supported by the Engineering and Physical Sciences Research Council (grants EP/L017008/1, EP/G03673X/1 and EP/J009016/1) and the European Research Council (grant 321305). I. D. W. S. acknowledges a Royal Society Wolfson Research Merit Award.Charge carrier photogeneration is studied in photovoltaic blends of the conjugated polymer PTB7 with the electron acceptor PC71BM at low excitation densities using broadband transient absorption spectroscopy. In the optimized blend we observe a rise of hole polaron absorption on a 500 ps time scale which implies an increase of hole delocalization when photo-generated charge pairs dissociate into free charges. This concept is supported by the observed saturation of polaron absorption with electrochemical oxidation of polymer films, and the significant differences in transient absorption spectra observed in an inefficient blend due to bound charge transfer (CT) states. Our results suggest that hole polaron delocalization on polymer chains and entropy provide driving force for charge separation by lowering the free energy of the spatially separated charge pair. A potential barrier to the reformation of CT states appears as a result of carrier delocalization which also helps to reduce non-geminate carrier recombination.Publisher PDFPeer reviewe

Ionic and electronic properties of the topological insulator Bi2_2Te2_2Se investigated using β\beta-detected nuclear magnetic relaxation and resonance of 8^8Li

We report measurements on the high temperature ionic and low temperature electronic properties of the 3D topological insulator Bi$_2$Te$_2$Se using ion-implanted $^8$Li $\beta$-detected nuclear magnetic relaxation and resonance. With implantation energies in the range 5-28 keV, the probes penetrate beyond the expected range of the topological surface state, but are still within 250 nm of the surface. At temperatures above ~150 K, spin-lattice relaxation measurements reveal isolated $^8$Li$^{+}$ diffusion with an activation energy $E_{A} = 0.185(8)$ eV and attempt frequency $\tau_{0}^{-1} = 8(3) \times 10^{11}$ s$^{-1}$ for atomic site-to-site hopping. At lower temperature, we find a linear Korringa-like relaxation mechanism with a field dependent slope and intercept, which is accompanied by an anomalous field dependence to the resonance shift. We suggest that these may be related to a strong contribution from orbital currents or the magnetic freezeout of charge carriers in this heavily compensated semiconductor, but that conventional theories are unable to account for the extent of the field dependence. Conventional NMR of the stable host nuclei may help elucidate their origin.Comment: 17 pages, 12 figures, submitted to Phys. Rev.

Risk of cardiovascular disease and total mortality in adults with type 1 diabetes: Scottish registry linkage study

<p>Background: Randomized controlled trials have shown the importance of tight glucose control in type 1 diabetes (T1DM), but few recent studies have evaluated the risk of cardiovascular disease (CVD) and all-cause mortality among adults with T1DM. We evaluated these risks in adults with T1DM compared with the non-diabetic population in a nationwide study from Scotland and examined control of CVD risk factors in those with T1DM.</p> <p>Methods and Findings: The Scottish Care Information-Diabetes Collaboration database was used to identify all people registered with T1DM and aged ≥20 years in 2005–2007 and to provide risk factor data. Major CVD events and deaths were obtained from the national hospital admissions database and death register. The age-adjusted incidence rate ratio (IRR) for CVD and mortality in T1DM (n = 21,789) versus the non-diabetic population (3.96 million) was estimated using Poisson regression. The age-adjusted IRR for first CVD event associated with T1DM versus the non-diabetic population was higher in women (3.0: 95% CI 2.4–3.8, p<0.001) than men (2.3: 2.0–2.7, p<0.001) while the IRR for all-cause mortality associated with T1DM was comparable at 2.6 (2.2–3.0, p<0.001) in men and 2.7 (2.2–3.4, p<0.001) in women. Between 2005–2007, among individuals with T1DM, 34 of 123 deaths among 10,173 who were <40 years and 37 of 907 deaths among 12,739 who were ≥40 years had an underlying cause of death of coma or diabetic ketoacidosis. Among individuals 60–69 years, approximately three extra deaths per 100 per year occurred among men with T1DM (28.51/1,000 person years at risk), and two per 100 per year for women (17.99/1,000 person years at risk). 28% of those with T1DM were current smokers, 13% achieved target HbA1c of <7% and 37% had very poor (≥9%) glycaemic control. Among those aged ≥40, 37% had blood pressures above even conservative targets (≥140/90 mmHg) and 39% of those ≥40 years were not on a statin. Although many of these risk factors were comparable to those previously reported in other developed countries, CVD and mortality rates may not be generalizable to other countries. Limitations included lack of information on the specific insulin therapy used.</p> <p>Conclusions: Although the relative risks for CVD and total mortality associated with T1DM in this population have declined relative to earlier studies, T1DM continues to be associated with higher CVD and death rates than the non-diabetic population. Risk factor management should be improved to further reduce risk but better treatment approaches for achieving good glycaemic control are badly needed.</p&gt

Development of an open-source, flexible framework for complex inter-institutional disparate data sharing and collaboration

Clinical information, “-omic” datasets, and tissue samples are difficult to harmonize and manage for data mining. We have developed a platform for storing clinical research data while providing access to associated data from other information stores. Data on 34 metrics from 11,000 neuroblastoma patients were instantiated into a database. The Django web framework was used to create a model for rapid development of tools and views with a front-end interface for generating complex queries. Working with Nationwide Children’s Hospital, we can now consume their tissue inventory data through an API. The end-user sees the number of patients who both match their search and have tissue available. Since initial implementation, the current tasks revolve around developing a governance structure and the necessary data use agreements. Efforts now are to (1) update the data with 5000 more patients, and (2) link to genomic data stores, facilitating disparate data acquisition for research studies

Patient stratification for determining optimal second-line and third-line therapy for type 2 diabetes:the TriMaster study

This is the author accepted manuscript. The final version is available from Nature Research via the DOI in this recordData availability: To minimize the risk of patient re-identification, de-identified individual patient-level clinical data are available under restricted access. Requests for access to anonymized individual participant data and study documents should be made to the corresponding author and will be reviewed by the Peninsula Research Bank Steering Committee. Access to data through the Peninsula Research Bank will be granted for requests with scientifically valid questions by academic teams with the necessary skills appropriate for the research. Data that can be shared will be released with the relevant transfer agreement.Code availability: Requests for access to code should be made to the corresponding author and will be reviewed by the Peninsula Research Bank Steering Committee. Access to code through the Peninsula Research Bank will be granted for requests with scientifically valid questions by academic teams with the necessary skills appropriate for the research. Code will be released by the lead statistician.Precision medicine aims to treat an individual based on their clinical characteristics. A differential drug response, critical to using these features for therapy selection, has never been examined directly in type 2 diabetes. In this study, we tested two hypotheses: (1) individuals with body mass index (BMI) > 30 kg/m2, compared to BMI ≤ 30 kg/m2, have greater glucose lowering with thiazolidinediones than with DPP4 inhibitors, and (2) individuals with estimated glomerular filtration rate (eGFR) 60-90 ml/min/1.73 m2, compared to eGFR >90 ml/min/1.73 m2, have greater glucose lowering with DPP4 inhibitors than with SGLT2 inhibitors. The primary endpoint for both hypotheses was the achieved HbA1c difference between strata for the two drugs. In total, 525 people with type 2 diabetes participated in this UK-based randomized, double-blind, three-way crossover trial of 16 weeks of treatment with each of sitagliptin 100 mg once daily, canagliflozin 100 mg once daily and pioglitazone 30 mg once daily added to metformin alone or metformin plus sulfonylurea. Overall, the achieved HbA1c was similar for the three drugs: pioglitazone 59.6 mmol/mol, sitagliptin 60.0 mmol/mol and canagliflozin 60.6 mmol/mol (P = 0.2). Participants with BMI > 30 kg/m2, compared to BMI ≤ 30 kg/m2, had a 2.88 mmol/mol (95% confidence interval (CI): 0.98, 4.79) lower HbA1c on pioglitazone than on sitagliptin (n = 356, P = 0.003). Participants with eGFR 60-90 ml/min/1.73 m2, compared to eGFR >90 ml/min/1.73 m2, had a 2.90 mmol/mol (95% CI: 1.19, 4.61) lower HbA1c on sitagliptin than on canagliflozin (n = 342, P = 0.001). There were 2,201 adverse events reported, and 447/525 (85%) randomized participants experienced an adverse event on at least one of the study drugs. In this precision medicine trial in type 2 diabetes, our findings support the use of simple, routinely available clinical measures to identify the drug class most likely to deliver the greatest glycemic reduction for a given patient. (ClinicalTrials.gov registration: NCT02653209 ; ISRCTN registration: 12039221 .).Medical Research Council (MRC)National Institute for Health and Care Research (NIHR