Palladium-Mediated¹¹C-Carbonylations Using Aryl Halides and Cyanamide

A robust and high-yielding radiochemical synthesis of ¹¹C-N-cyanobenzamides using a palladium-mediated aminocarbonylation with ¹¹C-CO, aryl halides and cyanamide is described. The bidentate ligand 1,1′-bis(diphenylphosphino)ferrocene provided ¹¹C-N-cyanobenzamides from aryl-iodides, bromides, triflates and even chlorides in 28–79% radiochemical yield after semi-preparative HPLC. To further highlight the utility of this method, novel ¹¹C-N-cyanobenzamide analogs of flufenamic acid, meflanamic acid, dazoxiben and tamibarotene were synthesized in 34–71% radiochemical yields

Tree-ring width wavelet and spectral analysis of solar variability and climatic effects on a Chilean cypress during the last two and a half millennia

International audienceSpectral and wavelet analysis were performed on a tree ring width time series obtained from a 2500 yr old cypress tree (Fitzroya cupressoides) from Costa del Osorno, Chile. The periods for analysis were selected at 95% confidence level. Both periodicities characteristic of solar activity and climatic variations were found in this tree ring width series. The 11 and 22 years solar cycle periods were present in tree ring data with a confidence level above 98%. This indicates the solar modulation of climatic variations is being recorded by the tree ring grown. However wavelet analysis shows that these are present only sparsely. Short-term variations, between 2-5 years, are also present in tree ring data, and are shown by wavelet maps to be a more permanent characteristic. This time scale is a signature of ENSO events. Long-term variations, above 200 years, are also present in tree ring data. The spectral analysis performed in this work shows that this species has the ability to record solar-ENSO variations that seems to be affecting the local environment of tree growth, and also that this region was influenced by ENSO events at least in the past 2500 yr interval covered by this study

Mild Pd-Catalyzed Aminocarbonylation of (Hetero)Aryl Bromides with a Palladacycle Precatalyst

A palladacyclic precatalyst is employed to cleanly generate a highly active XantPhos-ligated Pd-catalyst. Its use in low temperature aminocarbonylations of (hetero)aryl bromides provides access to a range of challenging products in good to excellent yields with low catalyst loading and only a slight excess of CO. Some products are unattainable by traditional carbonylative coupling.National Institutes of Health (U.S.) (Award GM46059)Danish National Research Foundation (Grant DNRF59)Villum FoundationDanish Council for Independent Researc

The clinical course of low back pain: a meta-analysis comparing outcomes in randomised clinical trials (RCTs) and observational studies.

BACKGROUND: Evidence suggests that the course of low back pain (LBP) symptoms in randomised clinical trials (RCTs) follows a pattern of large improvement regardless of the type of treatment. A similar pattern was independently observed in observational studies. However, there is an assumption that the clinical course of symptoms is particularly influenced in RCTs by mere participation in the trials. To test this assumption, the aim of our study was to compare the course of LBP in RCTs and observational studies. METHODS: Source of studies CENTRAL database for RCTs and MEDLINE, CINAHL, EMBASE and hand search of systematic reviews for cohort studies. Studies include individuals aged 18 or over, and concern non-specific LBP. Trials had to concern primary care treatments. Data were extracted on pain intensity. Meta-regression analysis was used to compare the pooled within-group change in pain in RCTs with that in cohort studies calculated as the standardised mean change (SMC). RESULTS: 70 RCTs and 19 cohort studies were included, out of 1134 and 653 identified respectively. LBP symptoms followed a similar course in RCTs and cohort studies: a rapid improvement in the first 6 weeks followed by a smaller further improvement until 52 weeks. There was no statistically significant difference in pooled SMC between RCTs and cohort studies at any time point:- 6 weeks: RCTs: SMC 1.0 (95% CI 0.9 to 1.0) and cohorts 1.2 (0.7to 1.7); 13 weeks: RCTs 1.2 (1.1 to 1.3) and cohorts 1.0 (0.8 to 1.3); 27 weeks: RCTs 1.1 (1.0 to 1.2) and cohorts 1.2 (0.8 to 1.7); 52 weeks: RCTs 0.9 (0.8 to 1.0) and cohorts 1.1 (0.8 to 1.6). CONCLUSIONS: The clinical course of LBP symptoms followed a pattern that was similar in RCTs and cohort observational studies. In addition to a shared 'natural history', enrolment of LBP patients in clinical studies is likely to provoke responses that reflect the nonspecific effects of seeking and receiving care, independent of the study design