A copper-catalyzed asymmetric oxime propargylation enables the synthesis of the gliovirin tetrahydro-1,2-oxazine core

The bicyclic tetrahydro-1,2-oxazine subunit of gliovirin is synthesized through a diastereoselective copper-catalyzed cyclization of an N-hydroxyamino ester. Oxidative elaboration to the fully functionalized bicycle was achieved through a series of mild transformations. Central to this approach was the development of the first catalytic, enantioselective propargylation of an oxime to furnish a key N-hydroyxamino ester intermediate

Long-Term Changes in Physical Activity Following a One-Year Home-Based Physical Activity Counseling Program in Older Adults with Multiple Morbidities

This study assessed the sustained effect of a physical activity (PA) counseling intervention on PA one year after intervention, predictors of sustained PA participation, and three classes of post-intervention PA trajectories (improvers, maintainers, and decliners) in 238 older Veterans. Declines in minutes of PA from 12 to 24 months were observed for both the treatment and control arms of the study. PA at 12 months was the strongest predictor of post-intervention changes in PA. To our surprise, those who took up the intervention and increased PA levels the most, had significant declines in post-intervention PA. Analysis of the three post-intervention PA trajectories demonstrated that the maintenance group actually reflected a group of nonresponders to the intervention who had more comorbidities, lower self-efficacy, and worse physical function than the improvers or decliners. Results suggest that behavioral counseling/support must be ongoing to promote maintenance. Strategies to promote PA appropriately to subgroups of individuals are needed

Effector-Triggered Immune Response in Arabidopsis thaliana Is a Quantitative Trait

We identified loci responsible for natural variation in Arabidopsis thaliana (Arabidopsis) responses to a bacterial pathogen virulence factor, HopAM1. HopAM1 is a type III effector protein secreted by the virulent Pseudomonas syringae strain Pto DC3000. Delivery of HopAM1 from disarmed Pseudomonas strains leads to local cell death, meristem chlorosis, or both, with varying intensities in different Arabidopsis accessions. These phenotypes are not associated with differences in bacterial growth restriction. We treated the two phenotypes as quantitative traits to identify host loci controlling responses to HopAM1. Genome-wide association (GWA) of 64 Arabidopsis accessions identified independent variants highly correlated with response to each phenotype. Quantitative trait locus (QTL) mapping in a recombinant inbred population between Bur-0 and Col-0 accessions revealed genetic linkage to regions distinct from the top GWA hits. Two major QTL associated with HopAM1-induced cell death were also associated with HopAM1-induced chlorosis. HopAM1-induced changes in Arabidopsis gene expression showed that rapid HopAM1-dependent cell death in Bur-0 is correlated with effector-triggered immune responses. Studies of the effect of mutations in known plant immune system genes showed, surprisingly, that both cell death and chlorosis phenotypes are enhanced by loss of EDS1, a regulatory hub in the plant immune-signaling network. Our results reveal complex genetic architecture for response to this particular type III virulence effector, in contrast to the typical monogenic control of cell death and disease resistance triggered by most type III effectors

What difference does a thiophene make? Evaluation of a 4,4′-bis(thiophene) functionalised 2,2′-bipyridyl copper(I) complex in a dye-sensitized solar cell

AbstractThe synthesis of a 4,4′-bis(2-thienyl-5-carboxylic acid) functionalised 2,2′-bipyridine ligand and corresponding copper(I) complex is described and its application in a dye-sensitized solar cell (DSSC) is studied. The positioning of the thiophene groups appears favourable from DFT analysis and a best efficiency of 1.41% was obtained with this dye, for a 0.3 cm2 cell area DSSC. Two absorbance bands are observed in the electronic absorption spectrum of the copper(I) complex at 316 nm and 506 nm, with ε values of 50,000 M−1 cm−1 and 9030 M−1 cm−1, respectively. Cyclic voltammetry and electrochemical impedance spectroscopy are also used to provide a detailed analysis of the dye and assess its functionality in a DSSC

What difference does a thiophene make? Evaluation of a 4,4′-bis(thiophene) functionalised 2,2′-bipyridyl copper(I) complex in a dye-sensitized solar cell

The synthesis of a 4,4′-bis(2-thienyl-5-carboxylic acid) functionalised 2,2′-bipyridine ligand and corresponding copper(I) complex is described and its application in a dye-sensitized solar cell (DSSC) is studied. The positioning of the thiophene groups appears favourable from DFT analysis and a best efficiency of 1.41% was obtained with this dye, for a 0.3 cm2 cell area DSSC. Two absorbance bands are observed in the electronic absorption spectrum of the copper(I) complex at 316 nm and 506 nm, with ε values of 50,000 M−1 cm−1 and 9030 M−1 cm−1, respectively. Cyclic voltammetry and electrochemical impedance spectroscopy are also used to provide a detailed analysis of the dye and assess its functionality in a DSSC

A copper-catalyzed asymmetric oxime propargylation enables the synthesis of the gliovirin tetrahydro-1,2-oxazine core

The bicyclic tetrahydro-1,2-oxazine subunit of gliovirin is synthesized through a diastereoselective copper-catalyzed cyclization of an N-hydroxyamino ester. Oxidative elaboration to the fully functionalized bicycle was achieved through a series of mild transformations. Central to this approach was the development of the first catalytic, enantioselective propargylation of an oxime to furnish a key N-hydroyxamino ester intermediate

Comparing Survival Following Hip Fracture Repair in VHA and Non-VHA Facilities

Introduction: Although postsurgical outcomes are similar between Veterans Health Administration (VHA) and non-VHA hospitals for many procedures, no studies have compared 30-day and 1-year survival following hip fracture repair. Therefore, this study compared survival of veterans aged 65 years and older treated in VHA hospitals with a propensity-matched cohort of Medicare beneficiaries in non-VHA hospitals. Materials and Methods: Retrospective cohort study of 1894 hip fracture repair patients in VHA or non-VHA hospitals between 2003 and 2005. Current Procedural Terminology codes identified 3542 male patients aged > 65 years who had hip fracture repair between 2003 and 2005 in the Veterans Affairs’ National Surgical Quality Improvement Program database. The Medicare comparison sample was drawn from 2003 to 2005 Medicare Part A inpatient hospital claims files. To create comparable VHA and Medicare cohorts, patients were propensity score matched on age, admission source (community vs. nursing home), repair type, comorbidity index, race, year, and region. Thirty-day and 1-year survival after surgery were compared between cohorts after further adjustment for selected comorbidities, year of surgery, and pre- and postsurgical length of hospital stay using logistic regression. Results: Odds of survival were significantly better in the Medicare than the VHA cohort at 30 days (1.68, 95% CI 1.15-2.44) and 1 year (1. 35 , 95% CI 1.08-1.69). Conclusion: Medicare beneficiaries with hip fracture repair in non-VHA hospitals had better survival than veterans in VHA hospitals. Whether this is driven by unobserved patient characteristics or systematic care differences is unknown

Long-Term Mortality of Older Patients With Acute Myocardial Infarction Treated in US Clinical Practice.

BackgroundThere is limited information about the long-term survival of older patients after myocardial infarction (MI).Methods and resultsCRUSADE (Can rapid risk stratification of unstable angina patients suppress adverse outcomes with early implementation of the ACC/AHA guidelines) was a registry of MI patients treated at 568 US hospitals from 2001 to 2006. We linked MI patients aged ≥65 years in CRUSADE to their Medicare data to ascertain long-term mortality (defined as 8 years post index event). Long-term unadjusted Kaplan-Meier mortality curves were examined among patients stratified by revascularization status. A landmark analysis conditioned on surviving the first year post-MI was conducted. We used multivariable Cox regression to compare mortality risks between ST-segment-elevation myocardial infarction and non-ST-segment-elevation myocardial infarction patients. Among 22 295 MI patients ≥ age 65 years (median age 77 years), we observed high rates of evidence-based medication use at discharge: aspirin 95%, β-blockers 94%, and statins 81%. Despite this, mortality rates were high: 24% at 1 year, 51% at 5 years, and 65% at 8 years. Eight-year mortality remained high among patients who underwent percutaneous coronary intervention (49%), coronary artery bypass graft (46%), and among patients who survived the first year post-MI (59%). Median survival was 4.8 years (25th, 75th percentiles 1.1, 8.5); among patients aged 65-74 years it was 8.2 years (3.3, 8.9) while for patients aged ≥75 years it was 3.1 years (0.6, 7.6). Eight-year mortality was lower among ST-segment-elevation myocardial infarction than non-ST-segment-elevation myocardial infarction patients (53% versus 67%); this difference was not significant after adjustment (hazard ratio 0.94, 95% confidence interval, 0.88-1.00).ConclusionsLong-term mortality remains high among patients with MI in routine clinical practice, even among revascularized patients and those who survived the first year