Depth-resolved characterization of Meissner screening breakdown in surface treated niobium.

We report direct measurements of the magnetic field screening at the limits of the Meissner phase for two superconducting niobium (Nb) samples. The samples are processed with two different surface treatments that have been developed for superconducting radio-frequency (SRF) cavity applications-a "baseline" treatment and an oxygen-doping ("O-doping") treatment. The measurements show: (1) that the screening length is significantly longer in the "O-doping" sample compared to the "baseline" sample; (2) that the screening length near the limits of the Meissner phase increases with applied field; (3) the evolution of the screening profile as the material transitions from the Meissner phase to the mixed phase; and (4) a demonstration of the absence of any screening profile for the highest applied field, indicative of the full flux entering the sample.

A multicenter evaluation of the time and travel burden on families with children treated for early-onset scoliosis.

Purpose: Patients who undergo growth-friendly (GF) treatment for early-onset scoliosis (EOS) undergo multiple clinical and surgical encounters. We sought to quantify the associated temporal and travel burden and estimate subsequent cost.

Methods: Four centers in an international study group combined data on EOS patients who underwent surgical GF treatment from 2006 to 2021.

Adaptive Biobehavioral Control: A Pilot Analysis of Human-Machine Coadaptation in Type 1 Diabetes.

While it is well recognized that an automated insulin delivery (AID) algorithm should adapt to changes in physiology, it is less understood that the individual would also have to adapt to the AID system. The adaptive biobehavioral control (ABC) method presented here attempts to compensate for this deficiency by including AID into an information cloud-based ecosystem. The Web Information Tool (WIT) implements the ABC concept via the following: (1) a Physiological Adaptation Module (PAM) that tracks metabolic changes and adapts AID parameters accordingly and (2) a Behavioral Adaptation Module (BAM) that provides information feedback.

Intraoperative Radiation Exposure in Adolescent Idiopathic and Neuromuscular Scoliosis.

Background: Intraoperative imaging is often used to aid pedicle screw placement during scoliosis operations. Higher rates of cancer and death have been observed in orthopaedic surgeons and radiation technologists, including a fourfold higher rate of breast cancer in female orthopaedic surgeons. The purpose of this study was to evaluate variability in intraoperative radiation during spinal fusions for both adolescent idiopathic scoliosis (AIS) and neuromuscular scoliosis (NMS).

A new high parallel-field spectrometer at TRIUMF's β-NMR facility.

A new high field spectrometer has been built to extend the capabilities of the β-detected nuclear magnetic resonance (β-NMR) facility at TRIUMF. This new beamline extension allows β-NMR spectroscopy to be performed with fields up to 200 mT parallel to a sample's surface (perpendicular to the ion beam), allowing depth-resolved studies of local electromagnetic fields with spin polarized probes at a much higher applied magnetic field than previously available in this configuration. The primary motivation and application is to allow studies of superconducting radio frequency (SRF) materials close to the critical fields of Nb metal, which is extensively used to fabricate SRF cavities.

Evaluation of a Web-Based Simulation Tool for Self-Management Support in Type 1 Diabetes: A Pilot Study.

Objective: To develop and evaluate a novel Web-based Simulation Tool (WST) that brings simulation technologies to people with Type 1 Diabetes (T1D), enabling unique patient-data interactions seamlessly on a daily basis.

Methods: A pilot clinical trial was conducted to assess system usability. The study consisted of one week of observation (Phase 1) and four weeks of interaction with WST (Phase 2).

Magnesium(II)-ATP Complexes in 1-Ethyl-3-Methylimidazolium Acetate Solutions Characterized by Mg β-Radiation-Detected NMR Spectroscopy.

The complexation of Mg with adenosine 5'-triphosphate (ATP) is omnipresent in biochemical energy conversion, but is difficult to interrogate directly. Here we use the spin- β-emitter Mg to study Mg -ATP complexation in 1-ethyl-3-methylimidazolium acetate (EMIM-Ac) solutions using β-radiation-detected nuclear magnetic resonance (β-NMR). We demonstrate that (nuclear) spin-polarized Mg, following ion-implantation from an accelerator beamline into EMIM-Ac, binds to ATP within its radioactive lifetime before depolarizing.

Accuracy of a Factory-Calibrated Continuous Glucose Monitor in Individuals With Diabetes on Hemodialysis.

Objective: Continuous glucose monitoring (CGM) improves diabetes management, but its reliability in individuals on hemodialysis is poorly understood and potentially affected by interstitial and intravascular volume variations.

Research Design And Methods: We assessed the accuracy of a factory-calibrated CGM by using venous blood glucose measurements (vBGM) during hemodialysis sessions and self-monitoring blood glucose (SMBG) at home.

Results: Twenty participants completed the protocol.

A β-NMR study of the depth, temperature, and molecular-weight dependence of secondary dynamics in polystyrene: Entropy-enthalpy compensation and dynamic gradients near the free surface.

We investigated the depth, temperature, and molecular-weight (MW) dependence of the γ-relaxation in polystyrene glasses using implanted Li and β-detected nuclear magnetic resonance. Measurements were performed on thin films with MW ranging from 1.1 to 641 kg/mol.

The Impact of a Recently Approved Automated Insulin Delivery System on Glycemic, Sleep, and Psychosocial Outcomes in Older Adults With Type 1 Diabetes: A Pilot Study.

Background: Older adults with type 1 diabetes (≥65 years) are often under-represented in clinical trials of automated insulin delivery (AID) systems. We sought to test the efficacy of a recently FDA-approved AID system in this population.

Methods: Participants with type 1 diabetes used sensor-augmented pump (SAP) therapy for four weeks and then used an AID system (Control-IQ) for four weeks.

Sleep and diabetes-specific psycho-behavioral outcomes of a new automated insulin delivery system in young children with type 1 diabetes and their parents.

Background: Data on the use of Control-IQ, the latest FDA-approved automated insulin delivery (AID) system for people with T1D 6 years of age or older is still scarce, particularly regarding nonglycemic outcomes. Children with T1D and their parents are at higher risk for sleep disturbances. This study assesses sleep, psycho-behavioral and glycemic outcomes of AID compared to sensor-augmented pump therapy (SAP) therapy in young children with T1D and their parents.

Titanium for Orthopedic Applications: An Overview of Surface Modification to Improve Biocompatibility and Prevent Bacterial Biofilm Formation.

Titanium and its alloys have emerged as excellent candidates for use as orthopedic biomaterials. Nevertheless, there are often complications arising after implantation of orthopedic devices, most notably prosthetic joint infection and aseptic loosening. To ensure that implanted devices remain functional , innovation in surface modification has attracted much attention in the effort to develop orthopedic materials with optimal characteristics at the biomaterial-tissue interface.

Investigation of ionic and anomalous magnetic behavior in CrSe using Li β-NMR.

We have studied a mosaic of 1T-CrSe single crystals using β-detected nuclear magnetic resonance of Li from 4 to 300 K. We identify two broad resonances that show no evidence of quadrupolar splitting, indicating two magnetically distinct environments for the implanted ion. We observe stretched exponential spin lattice relaxation and a corresponding rate (1/ ) that increases monotonically above 200 K, consistent with the onset of ionic diffusion.

Direct observation of Mg complexes in ionic liquid solutions by Mg β-NMR spectroscopy.

NMR spectra of Mg2+ ions in ionic liquids were recorded using a highly sensitive variant of NMR spectroscopy known as β-NMR. The β-NMR spectra of MgCl2 in EMIM-Ac and EMIM-DCA compare favourably with conventional NMR, and exhibit linewidths of ∼3 ppm, allowing for discrimination of species with oxygen and nitrogen coordination.

Direct measurements of the temperature, depth and processing dependence of phenyl ring dynamics in polystyrene thin films by β-detected NMR.

There is indirect evidence that the dynamics of a polymer near a free surface are enhanced compared with the bulk but there are few studies of how dynamics varies with depth. β-Detected nuclear spin relaxation of implanted 8Li+ has been used to directly probe the temperature and depth dependence of the γ-relaxation mode, which is due to phenyl rings undergoing restricted rotation, in thin films of atactic deuterated polystyrene (PS-d8) and determine how the depth dependence of dynamics is affected by sample processing, such as annealing, floating on water and the inclusion of a surfactant, and by the presence of a buried interface. The activation energy for the γ-relaxation process is lower near the free surface.

β-NMR measurements of molecular-scale lithium-ion dynamics in poly(ethylene oxide)-lithium-salt thin films.

β-detected NMR (β-NMR) has been used to study the molecular-scale dynamics of lithium ions in thin films of poly(ethylene oxide) (PEO) containing either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium trifluoroacetate (LiTFA) salts at monomer-to-salt ratios (EO/Li) of 8.3. The results are compared with previous β-NMR measurements on pure PEO and PEO with lithium triflate (LiOTf) at the same loading [McKenzie et al.

Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation.

Pd-catalyzed enantioselective alkylation in conjunction with further synthetic elaboration enables the formal total syntheses of a number of "classic" natural product target molecules. This publication highlights recent methods for setting quaternary and tetrasubstituted tertiary carbon stereocenters to address the synthetic hurdles encountered over many decades across multiple compound classes spanning carbohydrate derivatives, terpenes, and alkaloids. These enantioselective methods will impact both academic and industrial settings, where the synthesis of stereogenic quaternary carbons is a continuing challenge.

Selective free radical reactions using supercritical carbon dioxide.

We report herein a means to modify the reactivity of alkenes, and particularly to modify their selectivity toward reactions with nonpolar reactants (e.g., nonpolar free radicals) in supercritical carbon dioxide near the critical point.

Identification and optimization of pteridinone Toll-like receptor 7 (TLR7) agonists for the oral treatment of viral hepatitis.

Pteridinone-based Toll-like receptor 7 (TLR7) agonists were identified as potent and selective alternatives to the previously reported adenine-based agonists, leading to the discovery of GS-9620. Analogues were optimized for the immunomodulatory activity and selectivity versus other TLRs, based on differential induction of key cytokines including interferon α (IFN-α) and tumor necrosis factor α (TNF-α). In addition, physicochemical properties were adjusted to achieve desirable in vivo pharmacokinetic and pharmacodynamic properties.

Radical kinetics in sub- and supercritical carbon dioxide: thermodynamic rate tuning.

We report rate constants for muonium addition to 1,1-difluoroethylene (vinylidene fluoride) in CO2 at 290-530 K, 40-360 bar, and 0.05-0.90 g cm(-3).

Enantioselective decarboxylative alkylation reactions: catalyst development, substrate scope, and mechanistic studies.

α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity.

The catalytic enantioselective total synthesis of (+)-liphagal.

[Image: see text] : The first catalytic enantioselective total synthesis of the meroterpenoid natural product (+)-liphagal is disclosed. The approach showcases a variety of technology including enantioselective enolate alkylation, a photochemical alkyne-alkene [2+2] reaction, microwave-assisted metal catalysis, and an intramolecular aryne capture cyclization reaction. Pivotal to the successful completion of the synthesis was a sequence involving ring expansion from a [6-5-4] tricycle to a [6-7] bicyclic core followed by stereoselective hydrogenation of a sterically occluded tri-substituted olefin to establish the trans homodecalin system found in the natural product.

The palladium-catalyzed aerobic kinetic resolution of secondary alcohols: reaction development, scope, and applications.

The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions.

A facile and modular synthesis of phosphinooxazoline ligands.

The copper(I) iodide catalyzed phosphine/aryl halide coupling procedure of Buchwald et al. provides modular, robust, and scaleable access to phosphinooxazoline (PHOX) ligands. The advantages of this method are highlighted by the convenient synthesis of PHOX ligands with varied steric and electronic properties, which would be challenging to synthesize by other protocols.