The synthetic utility of tetrabenzyl pyrophosphate for achieving chemoselective phosphorylation of phenols, as well as primary, secondary, and tertiary alcohols, is reported here. Additionally, we introduce a rapid, mild, and chemoselective debenzylation procedure, enabling access to phosphates in the presence of redox sensitive groups. Finally, stoichiometrically controlled monodebenzylation provides a versatile platform for late-stage divergent synthesis of phosphodiester and phosphoramidate chemical libraries.
View Article and Find Full Text PDFChiral aziridines are important structural motifs found in natural products and various target molecules. They serve as versatile building blocks for the synthesis of chiral amines. While advances in catalyst design have enabled robust methods for enantioselective aziridination of activated olefins, simple and abundant alkyl-substituted olefins pose a significant challenge.
View Article and Find Full Text PDFPlanar chirality is an important form of molecular chirality that can be utilized to induce enantioselectivity when incorporated into transition metal catalysts. However, due to synthetic constraints, the use of late transition metal planar chiral complexes to conduct enantioselective transformations has been limited. Additionally, the published methods surrounding the stereochemical assignment of planar chiral compounds are sometimes conflicting, making proper assignment difficult.
View Article and Find Full Text PDFRibosomally synthesized and post-translationally modified peptides (RiPPs) are known for their macrocyclic structures, which impart unique biological activity. One rapidly emerging subclass of RiPP natural products contains macrocyclic C-C cross-links between two amino acid side chains. These linkages, often biosynthetically formed by a single rSAM or P450 enzyme, introduce significant structural and synthetic complexity to the molecules.
View Article and Find Full Text PDFBackground: Inability to adhere to nutritional recommendations is common and linked to worse outcomes in patients with nutrition-sensitive conditions.
Objectives: The purpose of this study is to evaluate whether medically tailored meals (MTMs) improve outcomes in recently discharged adults with nutrition-sensitive conditions compared with usual care.
Research Design: Remote pragmatic randomized trial.
Introduction: Monitoring hospital mortality using retrospective case record review (RCRR) is being adopted throughout the National Health Service (NHS) in England with publication of estimates of avoidable mortality beginning in 2017. We describe our experience of reviewing the care records of inpatients who died following admission to hospital in four acute hospital NHS Foundation Trusts in the North-East of England.
Methods: RCRR of 7370 patients who died between January 2012 and December 2015.
We describe novel CHRDL1 mutations in ten families with X-linked megalocornea (MGC1). Our mutation-positive cohort enabled us to establish ultrasonography as a reliable clinical diagnostic tool to distinguish between MGC1 and primary congenital glaucoma (PCG). Megalocornea is also a feature of Neuhäuser or megalocornea-mental retardation (MMR) syndrome, a rare condition of unknown etiology.
View Article and Find Full Text PDFDespite the eye being surrounded by orbital bones and protective mechanisms such as the blink reflex, it is vulnerable to trauma. The two key issues to consider when presented with a case of ocular trauma are the visual potential of the eye and the risk of sympathetic ophthalmia. The Ocular Trauma Score can be used to assess the visual potential of the injured eye.
View Article and Find Full Text PDFThe evidence is inconclusive as to whether better patient outcomes for behavioral issues in acute care are achieved using constant patient observation. Nurse leaders at a northern California hospital designed and implemented proactive strategies to identify patients at risk for behavioral issues, developed evidence-based interventions to reduce the use of sitters and constant observation, and maintained or improved patient safety.
View Article and Find Full Text PDFAffinity is a computerized assessment tool that combines viewing time and self-report measures of sexual interest. The present study was designed to assess the diagnostic properties of Affinity with respect to sexual interest in prepubescent children. Reliability of both self-report and viewing time components was estimated to be high.
View Article and Find Full Text PDFIn 1987, Ramos-Arroyo et al. described a family with a previously unreported combination of features, which included corneal anesthesia, short stature, sensorineural deafness, learning difficulties, and a characteristic facial appearance. The family was reviewed in 2008 and additional features were noted.
View Article and Find Full Text PDFWe show that a label-free electrochemical method can be used to monitor the position of an enriched analyte band during bipolar electrode focusing in a microfluidic device. The method relies on formation of a depleted buffer cation region, which is responsible for concentration enrichment of the charged analyte. However, this depletion region also leads to an increase in the local electric field in the solution near a bipolar electrode (BPE), and this in turn results in enhanced faradaic reactions (oxidation and reduction of water) at the BPE.
View Article and Find Full Text PDFOver the past decade, bipolar electrochemistry has emerged from relative obscurity to provide a promising new means for integrating electrochemistry into lab-on-a-chip systems. This article describes the fundamental operating principles of bipolar electrodes, as well as several interesting applications.
View Article and Find Full Text PDFTwo organometallic complexes having cyclopentadienyldiazonium ligands have been isolated and characterized by spectroscopy, X-ray crystallography, and electrochemistry. Both CoCp(η(5)-C(5)H(4)N(2))(2+) (2(2+)) and Mn(CO)(3)(η(5)-C(5)H(4)N(2))(+) (3(+)) undergo facile cyclopentadienyldiazonium ligand-based one-electron reductions which liberate dinitrogen and result in strong binding of the cyclopentadienyl ligand to a glassy carbon surface, similar to the processes well established for organic aryldiazonium salts. The organometallic-modified electrodes are robust and have a thickness of approximately one monolayer (Γ = (2-4) × 10(-10) mol cm(-2)).
View Article and Find Full Text PDFCommunication failures during shift reports are a leading cause of sentinel events in the United States. Providing adequate information during change-of-shift reporting is essential to promoting patient safety. In addition, patients want to be more involved in decisions regarding their plan of care.
View Article and Find Full Text PDFBipolar electrode focusing at discontinuous bipolar electrodes (BPEs) provides new insight into the faradaic current and electric field characteristics associated with the technique and allows for the controlled transport of a focused anionic tracer in a microfluidic channel. The findings corroborate our previously reported simulation results, which describe the formation of an extended electric field gradient leading to concentration enrichment. This gradient has been attributed to the passage of faradaic current through a BPE affixed to the floor of the microchannel.
View Article and Find Full Text PDFA method for simultaneously concentrating and separating analytes in a buffer-filled microfluidic channel is reported. The approach is based on modulation of the local electric field within the channel and the corresponding opposition of electrophoretic and electroosmotic flow (EOF) velocities. Dye molecules having different electrophoretic mobilities are focused at different locations within the channel where concentration takes place.
View Article and Find Full Text PDFBackground: Emergency abdominal aortic aneurysm (EmAAA) represents a spectrum of disease from symptomatic non-ruptured aneurysms to free intraperitoneal rupture, with significantly worse outcomes for patients in a haemodynamically shocked state before surgery. A study was undertaken to see if the preoperative journey and outcome were different in patients who deviated from the classic acutely shocked presentation.
Methods: An observational database compiled from case notes of patients undergoing surgery for EmAAA at Sunderland Royal Hospital between April 2000 and October 2006 was interrogated to examine details of patient preoperative journey, physiological status and 30-day survival.