Flexible and rigid core molecules in the synthesis of poly(lactic acid) star polymers

This study presents the synthesis and physical characterization of a series of structurally well-defined star-shaped poly(lactic acids). Polymer stars are prepared from a series of multifunctional alcohol cores including flexible polyols pentaerythritol and dipentaerythritol (four-armed and six-armed cores, respectively) and rigid substituted arenes tri(hydroxymethyl)benzene and hexa(hydroxymethyl)benzene. Utilizing a tin(II) octanoate catalyst, arms of 10 monomer units long are built from rac-lactide and l-lactide to form atactic and isotactic star polymers. Polymers were subsequently characterized by means of NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. Our results support previous work that suggests that the length of the individual arms, not the total molecular weight, correlates to physical characteristics including glass, melt, crystallization, and decomposition temperatures. In addition, differences between core molecules suggest that the chemical nature of the core can significantly alter the physical properties of the star polymer. Trends in crystallization and glass transition temperatures relative to the core used merit further study and correlate closest to the molecular weight and the number of arms emanating from the star core. It is also clear that the rigidity provided by aromatic cores has a significant effect on the melting temperatures of these macromolecules

Organometallic mediated radical polymerization

Controlled radical polymerization has become increasingly important over the past decade and a half, allowing for the facile synthesis of specific macromolecular architectures with excellent control over the chemical and physical properties. This article presents an organized and detailed review of one particular CRP technique, organometallic mediated radical polymerization (OMRP), focusing on the individual catalysts developed, their efficacy and monomer scope. Rhodium, cobalt, molybdenum, osmium, iron, palladium, titanium, chromium and vanadium mediated radical polymerizations are presented alongside organo-main group mediated reactions. A separate section reviews the types of copolymers which have been synthesized using OMRP techniques. An attempt is made to unify the many disparate names which have previously been used for OMRP by virtue of the common mechanistic aspects displayed by the different catalyst systems. A mechanistic discussion highlights the similarities and differences between these systems and examines the interplay between reversible termination and degenerative transfer OMRP and competing 1-electron redox processes

The impact of the UK COVID-19 pandemic on patient-reported health outcomes after stroke: a retrospective sequential comparison

BACKGROUND AND PURPOSE: The COVID-19 pandemic and related social isolation measures are likely to have adverse consequences on community healthcare provision and outcome after acute illnesses treated in hospital, including stroke. We aimed to evaluate the impact of the COVID-19 pandemic on patient-reported health outcomes after hospital admission for acute stroke. METHODS: This retrospective study included adults with acute stroke admitted to the University College Hospital NHS Foundation Trust Hyperacute Stroke Unit. We included two separate cohorts of consecutively enrolled patients from the same geographical population at two time points: 16th March-16th May 2018 (pre-COVID-19 pandemic); and 16th March-16th May 2020 (during the COVID-19 pandemic). Patients in both cohorts completed the validated Patient Reported Outcomes Measurement Information System-29 (PROMIS-29 version 2.0) at 30 days after stroke. RESULTS: We included 205 patients who were alive at 30 days (106 admitted before and 99 admitted during the COVID-19 pandemic), of whom 201/205 (98%) provided patient-reported health outcomes. After adjustment for confounding factors, admission with acute stroke during the COVID-19 pandemic was independently associated with increased anxiety (β = 28.0, p < 0.001), fatigue (β = 9.3, p < 0.001), depression (β = 4.5, p = 0.002), sleep disturbance (β = 2.3, p = 0.018), pain interference (β = 10.8, p < 0.001); and reduced physical function (β = 5.2, p < 0.001) and participation in social roles and activities (β = 6.9, p < 0.001). CONCLUSION: Compared with the pre-pandemic cohort, patients admitted with acute stroke during the first wave of the COVID-19 pandemic reported poorer health outcomes at 30 day follow-up in all domains. Stroke service planning for any future pandemic should include measures to mitigate this major adverse impact on patient health

Titanium pyridonates for the homo- and copolymerization of <i>rac</i>-lactide and ε-caprolactone

A series of titanium pyridonate complexes have been synthesized under very mild reaction conditions from a common precursor, Ti(NMe2)4. These complexes have been explored as initiators for the ring-opening polymerization of rac-lactide and ε-caprolactone and have proven to be competitive with leading titanium initiators.</p

Consensus: a framework for evaluation of uncertain gene variants in laboratory test reporting

Accurate interpretation of gene testing is a key component in customizing patient therapy. Where confirming evidence for a gene variant is lacking, computational prediction may be employed. A standardized framework, however, does not yet exist for quantitative evaluation of disease association for uncertain or novel gene variants in an objective manner. Here, complementary predictors for missense gene variants were incorporated into a weighted Consensus framework that includes calculated reference intervals from known disease outcomes. Data visualization for clinical reporting is also discussed

Effects of Antihypertensive Medications on Quality of Life in Elderly Hypertensive Women

The impact of antihypertensive medications on the quality of life of elderly hypertensive women has rarely been systematically evaluated in large clinical trials using drugs from the new generations of pharmaceutic preparations. We carried out a multicenter, randomized double-blind clinical trial with 309 hypertensive women aged 60 to 80 years to assess effects of atenolol, enalapril, and isradipine on measures of quality of life over a 22-week period. The patients had mild to moderate hypertension. Hydrochlorothiazide was added to treatment if monotherapy was inadequate in lowering blood pressure. At the conclusion of the trial the three drug groups did not differ in degree of reduction of diastolic blood pressure or in supplementation with hydrochlorothiazide. Over the 22-week trial, linear trend analysis showed no differences between the treatment groups in change from baseline on quality of life measures of well-being, physical status, emotional status, cognitive functioning, and social role participation. Regarding each of 33 physical side effects over the 22 weeks, we found no general difference between atenolol, enalapril, and isradipine groups on measures of change in distress over symptoms except for enalapril patients who worsened in distress over cough (P = .001) and atenolol patients who worsened in distress over dry mouth (P = .014). Centering on three medications that are relatively new additions to the armamentarium for blood pressure control, the findings underline the increasing opportunities for the physician to select drugs that can control blood pressure while maintaining the quality of life of elderly hypertensive women

Incident disease associations with mosaic chromosomal alterations on autosomes, X and Y chromosomes: insights from a phenome-wide association study in the UK Biobank.

BackgroundMosaic chromosomal alterations (mCAs) are large chromosomal gains, losses and copy-neutral losses of heterozygosity (LOH) in peripheral leukocytes. While many individuals with detectable mCAs have no notable adverse outcomes, mCA-associated gene dosage alterations as well as clonal expansion of mutated leukocyte clones could increase susceptibility to disease.ResultsWe performed a phenome-wide association study (PheWAS) using existing data from 482,396 UK Biobank (UKBB) participants to investigate potential associations between mCAs and incident disease. Of the 1290 ICD codes we examined, our adjusted analysis identified a total of 50 incident disease outcomes associated with mCAs at PheWAS significance levels. We observed striking differences in the diseases associated with each type of alteration, with autosomal mCAs most associated with increased hematologic malignancies, incident infections and possibly cancer therapy-related conditions. Alterations of chromosome X were associated with increased lymphoid leukemia risk and, mCAs of chromosome Y were linked to potential reduced metabolic disease risk.ConclusionsOur findings demonstrate that a wide range of diseases are potential sequelae of mCAs and highlight the critical importance of careful covariate adjustment in mCA disease association studies

Poincare Invariant Algebra From Instant to Light-Front Quantization

We present the Poincare algebra interpolating between instant and light-front time quantizations. The angular momentum operators satisfying SU(2) algebra are constructed in an arbitrary interpolation angle and shown to be identical to the ordinary angular momentum and Leutwyler-Stern angular momentum in the instant and light-front quantization limits, respectively. The exchange of the dynamical role between the transverse angular mometum and the boost operators is manifest in our newly constructed algebra.Comment: 21 pages, 3 figures, 1 tabl

Technical assessment of Mir-1 life support hardware for the international space station

NASA has been progressively learning the design and performance of the Russian life support systems utilized in their Mir space station. In 1992, a plan was implemented to assess the benefits of the Mir-1 life support systems to the Freedom program. Three primary tasks focused on: evaluating the operational Mir-1 support technologies and understanding if specific Russian systems could be directly utilized on the American space station and if Russian technology design information could prove useful in improving the current design of the planned American life support equipment; evaluating the ongoing Russian life support technology development activities to determine areas of potential long-term application to the U.S. space station; and utilizing the expertise of their space station life support systems to evaluate the benefits to the current U.S. space station program which included the integration of the Russian Mir-1 designs with the U.S. designs to support a crew of six