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1.
Functionalized reactive polymers for the removal of chemical warfare agents: A review.
Snider, VG, Hill, CL
Journal of hazardous materials. 2023;:130015
Abstract
Protection from and removal of chemical warfare agents (CWAs) from the environment remains a global goal. Activated charcoal, metal oxides, metal organic frameworks (MOFs), polyoxometalates (POMs) and reactive polymers have all been investigated for CWA removal. Composite polymeric materials are rapidly gaining traction as versatile building blocks for personal protective equipment (PPE) and catalytic devices. Polymers are inexpensive to produce and easily engineered into a wide range of materials including films, electro-spun fibers, mixed-matrix membranes/reactors, and other forms. When containing reactive side-chains, hydrolysis catalysts, and/or oxidative catalysts polymeric devices are primed for CWA decontamination. In this review, recent advances in reactive polymeric materials for CWA removal are summarized. To aid in comparing the effectiveness of the different solid catalysts, particular attention is paid to the stoichiometric ratio of reactive species to toxic substrate (CWA or CWA simulant).
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Efficacy and safety of colchicine for the treatment of osteoarthritis: a systematic review and meta-analysis of intervention trials.
Singh, A, Molina-Garcia, P, Hussain, S, Paul, A, Das, SK, Leung, YY, Hill, CL, Danda, D, Samuels, J, Antony, B
Clinical rheumatology. 2023;(3):889-902
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Abstract
OBJECTIVE Colchicine, an approved treatment for gout, has been trialed in many diseases including osteoarthritis (OA) due to its anti-inflammatory effects. However, its efficacy and safety remain unclear in OA. This systematic review and meta-analysis evaluated the efficacy and safety of colchicine for the treatment of OA. METHODS PubMed, Web of Science, Scopus, and Cochrane Central were searched from inception through September 2022. Two reviewers independently screened for randomized controlled trials (RCTs) comparing colchicine with placebo or other active comparators for the treatment of OA (knee, hand, or hip OA), extracted data, and performed Cochrane risk of bias assessments. RESULT Nine RCTs for the knee OA and one for the hand OA were identified, consisting of 847 patients (429 in colchicine arms, 409 in control arms). The studies were conducted between 2002 and 2021 with follow-up periods ranging from 2 to 12 months, in India, Iran, Turkey, Australia, Singapore, and Iraq. Moderate-quality evidence showed no clinically important pain reduction with colchicine compared to control (standardized mean difference [SMD], 0.17; 95% confidence interval [CI], - 0.55, 0.22). Moderate-quality evidence showed no improvement in function with colchicine compared to control in knee OA patients (SMD, - 0.37; 95% CI, - 0.87, 0.13). Colchicine showed an acceptable safety profile with AEs/SAEs comparable to control. CONCLUSION Current evidence does not suggest a benefit of colchicine in reducing pain and improving physical function in the overall cohort of hand/knee OA patients. Future trials should focus on the subgroups of OA patients with local or systemic inflammation and/or mineralization who might benefit from colchicine.
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Contemporary Treatment Patterns and Clinical Outcomes of Comorbid Diabetes Mellitus and HFrEF: The CHAMP-HF Registry.
Vaduganathan, M, Fonarow, GC, Greene, SJ, DeVore, AD, Kavati, A, Sikirica, S, Albert, NM, Duffy, CI, Hill, CL, Patterson, JH, et al
JACC. Heart failure. 2020;(6):469-480
Abstract
OBJECTIVES The purpose of this study was to characterize the clinical profile, treatment patterns, and clinical outcomes of patients with comorbid diabetes mellitus (DM) and heart failure with reduced ejection fraction (HFrEF) in a contemporary, real-world U.S. outpatient registry in the context of evolving treatment strategies. BACKGROUND Specific antihyperglycemic classes have differential risks and benefits with respect to HF. Limited data are available evaluating contemporary treatment patterns and outcomes of patients with comorbid DM and HFrEF. METHODS Among 4,970 patients with chronic HFrEF (≤40%) across 152 U.S. sites in the CHAMP-HF prospective, observational registry (2015 to 2017), we examined therapies and clinical outcomes by DM status. RESULTS Median age was 68 (58 to 75) years of age; 29% were women; 73.5% were white; and 64% had coronary artery disease. Overall, 42% (n = 2,085) had comorbid DM with a median hemoglobin A1c (HbA1c) level of 7.2% (interquartile range [IQR]: 6.4% to 8.3%). One-fourth of DM patients (24%) were not treated with an antihyperglycemic therapy. Most patients with DM were taking 1 (46%) or 2 (23%) antihyperglycemic therapies: metformin (40%); insulin (33%); sulfonylureas (24%); dipeptidyl peptidase-4 inhibitors (10%); glucagon-like peptide (GLP)-1 receptor agonists (4%); sodium-glucose cotransporter (SGLT)-2 inhibitors (2%); and thiazolidinediones (2%). Among patients with DM, 62%, 16%, 80%, and 33.5% were receiving any angiotensin-converting enzyme (ACE) inhibitor/angiotensin receptor blockers (ARBs), angiotensin receptor-neprilysin inhibitor (ARNI), β-blockers, or mineralocorticoid receptor antagonists (MRAs) at baseline, respectively. Among patients without DM, corresponding baseline rates were 65%, 15%, 80%, and 37%, respectively. Patients with or without DM were infrequently treated with guideline-directed HFrEF therapies at target doses (≤27% across classes). During median 15-month follow-up, patients with DM experienced higher rates of all-cause mortality or HF hospitalization (30% vs. 23%, respectively), independent of 11 pre-specified covariates (adjusted hazard ratio: 1.35 (95% confidence interval: 1.21 to 1.52); p < 0.001). CONCLUSIONS Despite higher risk-adjusted clinical event rates in patients with comorbid HFrEF and DM, guideline-directed medical therapies for both disease states are incomplete and represent an important target for quality improvement through multidisciplinary care pathways.
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Age-Related Differences in the Noninvasive Evaluation for Possible Coronary Artery Disease: Insights From the Prospective Multicenter Imaging Study for Evaluation of Chest Pain (PROMISE) Trial.
Lowenstern, A, Alexander, KP, Hill, CL, Alhanti, B, Pellikka, PA, Nanna, MG, Mehta, RH, Cooper, LS, Bullock-Palmer, RP, Hoffmann, U, et al
JAMA cardiology. 2020;(2):193-201
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Abstract
IMPORTANCE Although cardiovascular (CV) disease represents the leading cause of morbidity and mortality that increases with age, the best noninvasive test to identify older patients at risk for CV events remains unknown. OBJECTIVE To determine whether the prognostic utility of anatomic vs functional testing varies based on patient age. DESIGN, SETTING, AND PARTICIPANTS Prespecified analysis of the Prospective Multicenter Imaging Study for Evaluation of Chest Pain (PROMISE) study, which used a pragmatic comparative effectiveness design. Participants were enrolled from 193 sites across North America and comprised outpatients without known coronary artery disease (CAD) but with symptoms suggestive of CAD. Data were analyzed between October 2018 and April 2019. INTERVENTIONS Randomization to noninvasive testing with coronary computed tomographic angiography or functional testing. MAIN OUTCOMES AND MEASURES The composite of CV death/myocardial infarction (MI) over a median follow-up of 25 months. RESULTS Among 10 003 PROMISE patients, we included the 8966 who received the noninvasive test to which they were randomized and had interpretable results; 6378 (71.1%) were younger than 65 years, 2062 (23.0%) were between ages 65 and 74 years, and 526 (5.9%) were 75 years and older. More than half of participants were women (4720 of 8966 [52.6%]). Only a minority of patients were of nonwhite race/ethnicity, a proportion that was lower among the older age groups (1071 of 6378 [16.8%] for <65 years; 258 of 2062 [12.5%] for age 65-74 years; 41 of 526 [7.8%] for ≥75 years). Compared with patients younger than 65 years, older patients were more likely to have a positive test result (age 65-74 years: odds ratio, 1.65; 95% CI, 1.42-1.91; age ≥75 years: odds ratio, 2.32; 95% CI, 1.83-2.95), regardless of noninvasive test completed. A positive functional test result was not associated with CV death/MI in patients younger than 65 years (hazard ratio [HR], 1.09; 95% CI, 0.43-2.82) but it was among older patients (age 65-74 years: HR, 3.18; 95% CI, 1.44-7.01; age ≥75 years: HR, 6.55; 95% CI, 1.46-29.35). Conversely, a positive anatomic test result was associated with CV death/MI among patients younger than 65 years (HR, 3.04; 95% CI, 1.46-6.34) but not among older patients (age, 65-74 years: HR, 0.67; 95% CI, 0.15-2.94; age ≥75 years: HR, 1.07; 95% CI, 0.22-5.34; P for interaction = .01). An elevated coronary artery calcium score was predictive of events in patients younger than 65 years (HR, 2.73; 95% CI, 1.31-5.69) but not for older patients (age 65-74 years: HR, 0.44; 95% CI, 0.14-1.42; age ≥75 years: HR, 1.31; 95% CI, 0.25-6.88). CONCLUSIONS AND RELEVANCE Older patients with stable symptoms suggestive of CAD are more likely to have a positive noninvasive test result and more coronary artery calcium. However, only a positive functional test result was associated with risk of CV death/MI. Age-specific approaches to noninvasive evaluation of CAD should be further examined. TRIAL REGISTRATION ClinicalTrials.gov identifier: NCT01174550.
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Lateral Wedge Insoles for Reducing Biomechanical Risk Factors for Medial Knee Osteoarthritis Progression: A Systematic Review and Meta-Analysis.
Arnold, JB, Wong, DX, Jones, RK, Hill, CL, Thewlis, D
Arthritis care & research. 2016;(7):936-51
Abstract
OBJECTIVE Lateral wedge insoles are intended to reduce biomechanical risk factors of medial knee osteoarthritis (OA) progression, such as increased knee joint load; however, there has been no definitive consensus on this topic. The aim of this systematic review and meta-analysis was to establish the within-subject effects of lateral wedge insoles on knee joint load in people with medial knee OA during walking. METHODS Six databases were searched from inception until February 13, 2015. Included studies reported on the immediate biomechanical effects of lateral wedge insoles during walking in people with medial knee OA. Primary outcomes of interest relating to the biomechanical risk of disease progression were the first and second peak external knee adduction moment (EKAM) and knee adduction angular impulse (KAAI). Eligible studies were pooled using random-effects meta-analysis. RESULTS Eighteen studies were included with a total of 534 participants. Lateral wedge insoles resulted in a small but statistically significant reduction in the first peak EKAM (standardized mean difference [SMD] -0.19; 95% confidence interval [95% CI] -0.23, -0.15) and second peak EKAM (SMD -0.25; 95% CI -0.32, -0.19) with a low level of heterogeneity (I(2) = 5% and 30%, respectively). There was a favorable but small reduction in the KAAI with lateral wedge insoles (SMD -0.14; 95% CI -0.21, -0.07, I(2) = 31%). Risk of methodologic bias scores (quality index) ranged from 8 to 13 out of 16. CONCLUSION Lateral wedge insoles cause small reductions in the EKAM and KAAI during walking in people with medial knee OA. Current evidence demonstrates that lateral wedge insoles appear ineffective at attenuating structural changes in people with medial knee OA as a whole and may be better suited to targeted use in biomechanical phenotypes associated with larger reductions in knee load.
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Voltammetric determination of the reversible potentials for [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]10- over the pH range of 2-12: electrolyte dependence and implications for water oxidation catalysis.
Liu, Y, Guo, SX, Bond, AM, Zhang, J, Geletii, YV, Hill, CL
Inorganic chemistry. 2013;(20):11986-96
Abstract
Voltammetric studies of the Ru-containing polyoxometalate water oxidation molecular catalyst [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2](10-) ([1(γ-SiW10O36)2](10-) where 1 represents the {Ru4O4(OH)2(H2O)4} core and 1(0) stands for its initial form with all ruthenium centers in the oxidation state IV) have been carried out in aqueous media over a wide range of pH (2-12 using Britton-Robinson buffer) and ionic strength. Well-defined voltammograms in buffered media are only obtained when Frumkin double layer effects are suppressed by the presence of a sufficient concentration of additional supporting electrolyte (LiNO3, NaNO3, KNO3, Ca(NO3)2, Mg(NO3)2, MgSO4, or Na2SO4). A combination of data derived from dc cyclic, rotating disk electrode, and Fourier transformed large amplitude ac voltammetry allow the assignment of two processes related to reduction of the framework and the complete series of Ru(III/IV) and Ru(IV/V) redox processes and also provide their reversible potentials. Analysis of these data reveals that K(+) has a significantly stronger interaction with 1(1) (the number inside bracket stands for the number of electrons removed from 1(0)) than found for the other cations investigated, and hence its presence significantly alters the pH dependence of the 1(0)/1(1) reversible potential. Comparison of experimental data with theory developed in terms of equilibrium constants for process 1(0)/1(1) reveals that both H(+) and K(+) interact competitively with both 1(0) and 1(1). Importantly, reversible potential data reveal that (i) proton transfer does not necessarily need to be coupled to all electron transfer steps to achieve catalytic oxidation of water, (ii) the four-electron oxidized form, 1(4), is capable of oxidizing water under all conditions studied, and (iii) under some conditions, the three-electron oxidized form, 1(3), also exhibits considerable catalytic activity.
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Reduction of O2 to superoxide anion (O2.-) in water by heteropolytungstate cluster-anions.
Geletii, YV, Hill, CL, Atalla, RH, Weinstock, IA
Journal of the American Chemical Society. 2006;(51):17033-42
Abstract
Fundamental information concerning the mechanism of electron transfer from reduced heteropolytungstates (POM(red)) to O2, and the effect of donor-ion charge on reduction of O2 to superoxide anion (O2.-), is obtained using an isostructural series of 1e--reduced donors: alpha-X(n+)W12O40(9-n)-, X(n+) = Al3+, Si4+, P5+. For all three, a single rate expression is observed: -d[POM(red)]/dt = 2k12[POM(red)][O2], where k12 is for the rate-limiting electron transfer from POM(red) to O2. At pH 2 (175 mM ionic strength), k12 increases from 1.4 +/- 0.2 to 8.5 +/- 1 to 24 +/- 2 M-1s-1 as Xn+ is varied from P5+ (3red) to Si4+ (2red) to Al3+ (1red). Variable-pH data (for 1red) and solvent-kinetic isotope (KIE = kH/kD) data (all three ions) indicate that protonated superoxide (HO2.) is formed in two steps--electron transfer, followed by proton transfer (ET-PT mechanism--rather than via simultaneous proton-coupled electron transfer (PCET). Support for an outersphere mechanism is provided by agreement between experimental k12 values and those calculated using the Marcus cross relation. Further evidence is provided by the small variation in k12 observed when Xn+ is changed from P5+ to Si4+ to Al3+, and the driving force for formation of O2.- (aq), which increases as cluster-anion charge becomes more negative, increases by nearly +0.4 V (a decrease of >9 kcal mol-1 in DeltaG degrees ). The weak dependence of k12 on POM reduction potentials reflects the outersphere ET-PT mechanism: as the anions become more negatively charged, the "successor-complex" ion pairs are subject to larger anion-anion repulsions, in the order [(3(ox)3-)(O2.-)]4- < [(2(ox)4-)(O2.-)]5- < [(1(ox)5-)(O2.-)]6-. This reveals an inherent limitation to the use of heteropolytungstate charge and reduction potential to control rates of electron transfer to O2 under turnover conditions in catalysis.