Simultaneous switching of two different CO2-switchable amines in the same solution.

Most CO2-responsive systems operate by using a base in water that is expected to be mostly deprotonated when under an atmosphere of air and mostly protonated under an atmosphere of CO2. This concept has led to the development of many different CO2-responsive materials such as solvents, polymers, surfactants, and solutes. As CO2-responsive materials research continues, more complex systems may be developed, including systems containing two different bases with different basicities. Understanding the influence each base has on the protonation equilibrium of the other base is important for designing systems in which effective deprotonation and protonation occur. This article presents a model that can predict the solution pH and the % protonation of two different bases at various concentrations under air and CO2. Experimental data was collected to demonstrate the successful simultaneous switching of two amines and to evaluate the accuracy of the predictive model. The simultaneous switching of two different CO2-switchable amines in the same solution was determined to be possible but only if the amine concentrations and basicities are within certain ranges, and only if the pKaH values of the two bases differ by no more than 3 units.

The dynamics of fishing villages along the South Atlantic Coast of North America (ca. 5000-3000 years BP).

We present new chronologies that inform the timing and tempo of shell ring and shell mound construction on the South Atlantic Bight. Our project combines recently acquired dates with legacy radiocarbon dates from over 25 rings and mounds to provide a higher-resolution chronology regarding the occupation and formation of this larger landscape of the earliest fishing villages along the East Coast of the United States. We resolve the ordering and timing of occupation of these rings and mounds through Bayesian statistical modeling. These new models historicize and contextualize these shell rings in ways previously impossible. Specifically, our new chronologies of these villages indicate that the earliest villages were established prior to the invention of pottery. The early period of village establishment evidences isolated village rings, whereas later periods seem to have more villages, but these appear to have been relocated to other areas and/or islands over time. Shell mounds are fewer in number, are spread throughout the time period, and may represent special purpose sites compared to shell-rings. Once villages spread, they quickly adopted new technologies (i.e., pottery) and created new institutions and practiced village relocation, which allowed this way of life to persist for more than a thousand years.

Adaptive Catalysts for the Selective Hydrogenation of Bicyclic Heteroaromatics using Ruthenium Nanoparticles on a CO2 -Responsive Support.

Ruthenium nanoparticles (NPs) immobilized on an amine-functionalized polymer-grafted silica support act as adaptive catalysts for the hydrogenation of bicyclic heteroaromatics. Whereas full hydrogenation of benzofuran and quinoline derivatives is achieved under pure H2 , introducing CO2 into the H2 gas phase leads to an effective shutdown of the arene hydrogenation while preserving the activity for the hydrogenation of the heteroaromatic part. The selectivity switch originates from the generation of ammonium formate species on the surface of the materials by catalytic hydrogenation of CO2 . The CO2 hydrogenation is fully reversible, resulting in a robust and rapid switch between the two states of the catalyst adapting its performance in response to the feed gas composition. A variety of benzofuran and quinoline derivatives were hydrogenated to fully or partially saturated products in high selectivity and yields simply by altering the composition of the feed gas from H2 to H2 /CO2 . The adaptive catalytic system thus provides controlled access to valuable products using a single catalyst rather than two specific and distinct catalysts with static reactivity.

Endovascular Revascularization of Multi Segment Chronically Occluded ICA.

This case report describes a novel endovascular method for treating chronically occluded internal carotid artery (COICA). The patient is a 55-year-old male with vascular risk factors who presented to an outside institution with right-sided weakness and dysarthria, was diagnosed as having a stroke, and discharged with medical management. The patient's symptoms failed to improve throughout the week prompting him to visit another outside institution, where computed tomography (CT) angiography showed bilateral occlusion of the ICAs at their origins extending intracranially. The patient was then transferred to our hospital, where head CT revealed bilateral acute infarcts predominantly in the left centrum ovale/corona radiata and left temporoparietal region. CT perfusion showed a large area of hypoperfusion in the entire left hemisphere as well as part of the right hemisphere (mismatch volume of 438-526 mL). The patient had significant neurological deficits despite sustained high perfusion pressure, so the following morning, the patient was taken for angiography showing complete occlusion of the left ICA with support mostly from the left external carotid artery (ECA)/ophthalmic collateralization. The microcatheter was able to be advanced to the level of the ophthalmic segment of the left ICA, so the decision was made to proceed with stenting from the left ophthalmic ICA to the cervical ICA. Seven consecutive coronary-carotid stents were placed to essentially reconstruct the left ICA. Post-stenting, the patient was treated with an Integrilin drip and transitioned to Aspirin and Brilinta the following morning. The patient's symptoms markedly improved after the procedure. CT perfusion, as well as diffusion magnetic resonance imaging (MRI), revealed recovery of the patient's penumbra and stability of the existing infarcts despite the delayed nature of revascularization respectively. This is a rarely reported study in literature describing the successful deployment of multiple stents in recreating the ICA from its extracranial to intracranial portion.

A multi-proxy assessment of the impact of environmental instability on Late Holocene (4500-3800 BP) Native American villages of the Georgia coast.

Circular shell rings along the South Atlantic Coast of North America are the remnants of some of the earliest villages that emerged during the Late Archaic (5000-3000 BP). Many of these villages, however, were abandoned during the Terminal Late Archaic (ca 3800-3000 BP). We combine Bayesian chronological modeling with mollusk shell geochemistry and oyster paleobiology to understand the nature and timing of environmental change associated with the emergence and abandonment of circular shell ring villages on Sapelo Island, Georgia. Our Bayesian models indicate that Native Americans occupied the three Sapelo shell rings at varying times with some generational overlap. By the end of the complex's occupation, only Ring III was occupied before abandonment ca. 3845 BP. Ring III also consists of statistically smaller oysters harvested from less saline estuaries compared to earlier occupations. Integrating shell biochemical and paleobiological data with recent tree ring analyses shows a clear pattern of environmental fluctuations throughout the period in which the rings were occupied. We argue that as the environment became unstable around 4300 BP, aggregation at villages provided a way to effectively manage fisheries that are highly sensitive to environmental change. However, with the eventual collapse of oyster fisheries and subsequent rebound in environmental conditions ca. post-3800 BP, people dispersed from shell rings, and shifted to non-marine subsistence economies and other types of settlements. This study provides the most comprehensive evidence for correlations between large-scale environmental change and societal transformations on the Georgia coast during the Late Archaic period.

Social Determinants of Health Attenuate the Relationship Between Race and Ethnicity and White Matter Hyperintensity Severity but not Microbleed Presence in Patients with Intracerebral Hemorrhage.

BACKGROUND: The association between race and ethnicity and microvascular disease in patients with intracerebral hemorrhage (ICH) is unclear. We hypothesized that social determinants of health (SDOHs) mediate the relationship between race and ethnicity and severity of white matter hyperintensities (WMHs) and microbleeds in patients with ICH. METHODS: We performed a retrospective observational cohort study of patients with ICH at two tertiary care hospitals between 2013 and 2020 who underwent magnetic resonance imaging of the brain. Magnetic resonance imaging scans were evaluated for the presence of microbleeds and WMH severity (defined by the Fazekas scale; moderate to severe WMH defined as Fazekas scores 3-6). We assessed for associations between sex, race and ethnicity, employment status, median household income, education level, insurance status, and imaging biomarkers of microvascular disease. A mediation analysis was used to investigate the influence of SDOHs on the associations between race and imaging features. We assessed the relationship of all variables with discharge outcomes. RESULTS: We identified 233 patients (mean age 62 [SD 16]; 48% female) with ICH. Of these, 19% were Black non-Hispanic, 32% had a high school education or less, 21% required an interpreter, 11% were unemployed, and 6% were uninsured. Moderate to severe WMH, identified in 114 (50%) patients, was associated with age, Black non-Hispanic race and ethnicity, highest level of education, insurance status, and history of hypertension, hyperlipidemia, or diabetes (p < 0.05). In the mediation analysis, the proportion of the association between Black non-Hispanic race and ethnicity and the Fazekas score that was mediated by highest level of education was 65%. Microbleeds, present in 130 (57%) patients, was associated with age, highest level of education, and history of diabetes or hypertension (p < 0.05). Age, highest level of education, insurance status, and employment status were associated with discharge modified Rankin Scale scores of 3-6, but race and ethnicity was not. CONCLUSIONS: The association between Black non-Hispanic race and ethnicity and moderate to severe WMH lost significance after we adjusted for highest level of education, suggesting that SDOHs may mediate the association between race and ethnicity and microvascular disease.

Selectivity control in hydrogenation through adaptive catalysis using ruthenium nanoparticles on a CO2-responsive support.

With the advent of renewable carbon resources, multifunctional catalysts are becoming essential to hydrogenate selectively biomass-derived substrates and intermediates. However, the development of adaptive catalytic systems, that is, with reversibly adjustable reactivity, able to cope with the intermittence of renewable resources remains a challenge. Here, we report the preparation of a catalytic system designed to respond adaptively to feed gas composition in hydrogenation reactions. Ruthenium nanoparticles immobilized on amine-functionalized polymer-grafted silica act as active and stable catalysts for the hydrogenation of biomass-derived furfural acetone and related substrates. Hydrogenation of the carbonyl group is selectively switched on or off if pure H2 or a H2/CO2 mixture is used, respectively. The formation of alkylammonium formate species by the catalytic reaction of CO2 and H2 at the amine-functionalized support has been identified as the most likely molecular trigger for the selectivity switch. As this reaction is fully reversible, the catalyst performance responds almost in real time to the feed gas composition.

Etiologic Subtypes of Ischemic Stroke in SARS-CoV-2 Patients in a Cohort of New York City Hospitals.

Objective: To describe the ischemic stroke subtypes related to coronavirus disease 2019 (COVID-19) in a cohort of New York City hospitals and explore their etiopathogenesis. Background: Most neurological manifestations are non-focal, but few have reported the characteristics of ischemic strokes or investigated its pathophysiology. Methods: Data were collected prospectively April 1-April 15, 2020 from two centers in New York City to review possible ischemic stroke types seen in COVID-19-positive patients. Patient presentation, demographics, related vascular risk factors, associated laboratory markers, as well as imaging and outcomes were collected. Results: The age of patients ranged between 27 and 82 years. Approximately 81% of patients had known vascular risk factors, the commonest being hypertension (75%) followed by diabetes (50%) coronary disease or atrial fibrillation. Eight patients presented with large vessel occlusion (LVO) with median age 55 years (27-82) and all were male. Eight patients presented with non-LVO syndromes, with median age 65.5 years (59-82) and most were female (62.5%). Both groups were 50% African Americans and 37.5% South Asian. Both groups had similar D-dimer levels although other acute phase reactants/disease severity markers (Ferritin, CRP, procalcitonin) were higher in the LVO group. The LVO group also had a significantly higher mortality compared to the non-LVO group. The most common etiology was cryptogenic (6 patients) followed by small vessel occlusion (3 patients) and undetermined-unclassified (3 patients). For the remaining 4 patients, 2 were identified as cardioembolic and 2 with large artery atherosclerosis. Conclusion: COVID-19-related ischemic events can present as small vessel occlusions, branch emboli or large vessel occlusions. The most common etiology is cryptogenic. Patients with LVO syndromes tend to be younger, male and may have elevated acute inflammatory markers.

Acute stroke care in a New York City comprehensive stroke center during the COVID-19 pandemic.

BACKGROUND AND PURPOSE: The coronavirus disease-2019 (COVID-19) pandemic caused unprecedented demand and burden on emergency health care services in New York City. We aim to describe our experience providing acute stroke care at a comprehensive stroke center (CSC) and the impact of the pandemic on the quality of care for patients presenting with acute ischemic stroke (AIS). METHODS: We retrospectively analyzed data from a quality improvement registry of consecutive AIS patients at New York University Langone Health's CSC between 06/01/2019-05/15/2020. During the early stages of the pandemic, the acute stroke process was modified to incorporate COVID-19 screening, testing, and other precautionary measures. We compared stroke quality metrics including treatment times and discharge outcomes of AIS patients during the pandemic (03/012020-05/152020) compared with a historical pre-pandemic group (6/1/2019-2/29/2020). RESULTS: A total of 754 patients (pandemic-120; pre-pandemic-634) were admitted with a principal diagnosis of AIS; 198 (26.3%) received alteplase and/or mechanical thrombectomy. Despite longer median door to head CT times (16 vs 12 minutes; p = 0.05) and a trend towards longer door to groin puncture times (79.5 vs. 71 min, p = 0.06), the time to alteplase administration (36 vs 35 min; p = 0.83), door to reperfusion times (103 vs 97 min, p = 0.18) and defect-free care (95.2% vs 94.7%; p = 0.84) were similar in the pandemic and pre-pandemic groups. Successful recanalization rates (TICI≥2b) were also similar (82.6% vs. 86.7%, p = 0.48). After adjusting for stroke severity, age and a prior history of transient ischemic attack/stroke, pandemic patients had increased discharge mortality (adjusted OR 2.90 95% CI 1.77 - 7.17, p = 0.021) CONCLUSION: Despite unprecedented demands on emergency healthcare services, early multidisciplinary efforts to adapt the acute stroke treatment process resulted in keeping the stroke quality time metrics close to pre-pandemic levels. Future studies will be needed with a larger cohort comparing discharge and long-term outcomes between pre-pandemic and pandemic AIS patients.

Stroke Treatment Delay Limits Outcome After Mechanical Thrombectomy: Stratification by Arrival Time and ASPECTS.

BACKGROUND AND PURPOSE: Mechanical thrombectomy (MT) has helped many patients achieve functional independence. The effect of time-to-treatment based in specific epochs and as related to Alberta Stroke Program Early CT Score (ASPECTS) has not been established. The goal of the study was to evaluate the association between last known normal (LKN)-to-puncture time and good functional outcome. METHODS: We conducted a retrospective cohort study of prospectively collected acute ischemic stroke patients undergoing MT for large vessel occlusion. We used binary logistic regression models adjusted for age, Modified Treatment in Cerebral Ischemia score, initial National Institutes of Health Stroke Scale, and noncontrast CT ASPECTS to assess the association between LKN-to-puncture time and favorable outcome defined as Modified Rankin Score 0-2 on discharge. RESULTS: Among 421 patients, 328 were included in analysis. Increased LKN-to-puncture time was associated with decreased probability of good functional outcome (adjusted odds ratio [aOR] ratio per 15-minute delay = .98; 95% confidence interval [CI], .97-.99; P = .001). This was especially true when LKN-puncture time was 0-6 hours (aOR per 15-minute delay = .94; 95% CI, .89-.99; P = .05) or ASPECTS 8-10 (aOR = .98; 95% CI, .97-.99; P = .002) as opposed to when LKN-puncture time was 6-24 hours (aOR per 15-minute delay = .99; 95% CI, .97-1.00; P = .16) and ASPECTS <8 (aOR = .98; 95% CI, .93-1.03; P = .37). CONCLUSION: Decreased LKN-groin puncture time improves outcome particularly in those with good ASPECTS presenting within 6 hours. Strategies to decrease reperfusion times should be investigated, particularly in those in the early time window and with good ASPECTS.

SARS-CoV-2 and Stroke in a New York Healthcare System.

BACKGROUND AND PURPOSE: With the spread of coronavirus disease 2019 (COVID-19) during the current worldwide pandemic, there is mounting evidence that patients affected by the illness may develop clinically significant coagulopathy with thromboembolic complications including ischemic stroke. However, there is limited data on the clinical characteristics, stroke mechanism, and outcomes of patients who have a stroke and COVID-19. METHODS: We conducted a retrospective cohort study of consecutive patients with ischemic stroke who were hospitalized between March 15, 2020, and April 19, 2020, within a major health system in New York, the current global epicenter of the pandemic. We compared the clinical characteristics of stroke patients with a concurrent diagnosis of COVID-19 to stroke patients without COVID-19 (contemporary controls). In addition, we compared patients to a historical cohort of patients with ischemic stroke discharged from our hospital system between March 15, 2019, and April 15, 2019 (historical controls). RESULTS: During the study period in 2020, out of 3556 hospitalized patients with diagnosis of COVID-19 infection, 32 patients (0.9%) had imaging proven ischemic stroke. Cryptogenic stroke was more common in patients with COVID-19 (65.6%) as compared to contemporary controls (30.4%, P=0.003) and historical controls (25.0%, P<0.001). When compared with contemporary controls, COVID-19 positive patients had higher admission National Institutes of Health Stroke Scale score and higher peak D-dimer levels. When compared with historical controls, COVID-19 positive patients were more likely to be younger men with elevated troponin, higher admission National Institutes of Health Stroke Scale score, and higher erythrocyte sedimentation rate. Patients with COVID-19 and stroke had significantly higher mortality than historical and contemporary controls. CONCLUSIONS: We observed a low rate of imaging-confirmed ischemic stroke in hospitalized patients with COVID-19. Most strokes were cryptogenic, possibly related to an acquired hypercoagulability, and mortality was increased. Studies are needed to determine the utility of therapeutic anticoagulation for stroke and other thrombotic event prevention in patients with COVID-19.

Carotid intimal sarcoma causing stroke and intracranial metastasis via tumor embolization.

OBJECTIVE: To present the clinical, radiologic, and pathologic findings of a patient with carotid intimal sarcoma. METHODS: Detailed medical interview, neurologic examination, and diagnostic evaluation including CT angiography head and neck, MRI brain and neck, digital subtraction angiography, and biopsy of the mass were performed. RESULTS: We report a patient who presented with symptoms of multifocal, bilateral strokes over weeks caused by an enlarging tumor thrombus associated with an intimal sarcoma of the carotid artery. The presence of a carotid space mass encasing the left internal carotid artery was initially not recognized on imaging and was mistakenly attributed to soft atheromatous plaque rather than tumor thrombus. Rapid disease progression resulted in multiple intracranial metastases from tumor embolization. CONCLUSION: Clinical and radiologic findings of intimal sarcoma may be similar to those of thrombotic disease. However, patients with sarcoma may show an associated perivascular soft tissue mass and an unusual distribution of vessel stenosis. Reevaluation of imaging should be considered in patients presenting with initial imaging findings suggestive of rapidly progressive thrombotic disease who have a poor response to antithrombotic therapy and do not follow an expected clinical course.

Early metal use and crematory practices in the American Southeast.

Long-distance exchange of copper objects during the Archaic Period (ca. 8000-3000 cal B.P.) is a bellwether of emergent social complexity in the Eastern Woodlands. Originating from the Great Lakes, the Canadian Maritimes, and the Appalachian Mountains, Archaic-age copper is found in significant amounts as far south as Tennessee and in isolated pockets at major trade centers in Louisiana but is absent from most of the southeastern United States. Here we report the discovery of a copper band found with the cremated remains of at least seven individuals buried in the direct center of a Late Archaic shell ring located in coastal Georgia. Late Archaic shell rings are massive circular middens thought to be constructed, in part, during large-scale ritual gatherings and feasting events. The exotic copper and cremated remains are unique in coastal South Carolina and Georgia where Archaic-age cremations are conspicuously absent and no other Archaic copper objects have been reported. Elemental data produced through laser ablation inductively coupled plasma mass spectrometry shows the copper originated from the Great Lakes, effectively extending Archaic copper exchange almost 1,000 km beyond its traditional boundaries. Similarities in mortuary practices and the presence of copper originating from the Great Lakes reveal the presence of long-distance exchange relations spanning vast portions of the eastern United States and suggest an unexpected level of societal complexity at shell ring localities. These findings are consistent with the hypothesis that elite actors solidified their positions through ritual gatherings and the long-distance exchange of exotic objects during the Archaic.

Zika Virus-Associated Guillain-Barré Syndrome in a Returning US Traveler.

Zika virus (ZIKV) infection has been associated with Guillain-Barré Syndrome (GBS). Roughly 60% of people in countries such as the U.S. live in areas at risk for seasonal spread of ZIKV. ZIKV belongs to a class of diseases that is not typically seen in hospital settings across the U.S. and Europe. We describe the case presentation, management, and treatment of ZIKV infection complicated by GBS. A 64-year-old woman with recent travel to the Dominican Republic presented with rash followed by an acute, ascending polyneuropathy consistent with GBS. She was confirmed to have an acute ZIKV infection by detection of ZIKV nucleic acid by reverse transcription-polymerase chain reaction. She met Brighton Collaboration criteria level 1 evidence for GBS. She received two courses of intravenous immunoglobulin and slowly improved, though still had weakness at discharge. More research is needed to identify the pathophysiology behind ZIKV-associated GBS and its optimal treatment. Prevention is fundamental to limiting infection and spread of ZIKV.

Intraobserver and interobserver variability of renal volume measurements in polycystic kidney disease using a semiautomated MR segmentation algorithm.

OBJECTIVE: Total renal volume and changes in kidney volume are markers of disease progression in autosomal-dominant polycystic kidney disease (ADPKD) but are not used in clinical practice in part because of the complexity of manual measurements. This study aims to assess the intra- and interobserver reproducibility of a semiautomated renal volumetric algorithm using fluid-sensitive MRI pulse sequences. SUBJECTS AND METHODS: Renal volumes of 17 patients with ADPKD were segmented from high-resolution coronal HASTE and true fast imaging with steady-state precession (FISP) MR acquisitions. Measurements performed independently by four readers were repeated, typically after 7 days. Intraobserver agreement indexes were calculated for total kidney volume for each patient. Interobserver agreement indexes were obtained for the six paired combinations of readers as well as for two readers after rigorous formalized training. Pearson and concordance correlation coefficients, coefficients of variation (CVs), and 95% limits of agreement were determined. RESULTS: The HASTE and true FISP sequences performed similarly with a median intraobserver agreement of greater than 98.1% and a CV of less than 2.4% across all readers. The median interobserver agreement was greater than 95.2% and the CV was less than 7.1%, across all reader pairs. Reader training further lowered interobserver CV. The mean total kidney volume was 1420 mL (range, 331-3782 mL) for HASTE imaging and 1445 mL (range, 301-3714 mL) for true FISP imaging, with mean image processing times per patient of 43 and 28 minutes, respectively. CONCLUSION: This semiautomated MR volumetric algorithm provided excellent intraobserver and very good interobserver reproducibility using fluid-sensitive pulse sequences that emphasize cyst conspicuity.

Glossary of the World Trade Organisation and public health: part 1

It presents the article that approaches the glossary of World Trade Organization and its relations with public health.

Glossary on the World Trade Organisation and public health: part 2.

Part 1 of this glossary introduced different health and trade arguments, overviewed the history of the World Trade Organisation (WTO), defined key "trade talk" terms, and reviewed three WTO treaties concerned with trade in goods (GATT 1994, the Agreement on Agriculture, and the Agreement on Sanitary and Phytosanitary Measures). Part 2 reviews five more agreements and the growing number of bilateral and regional trade agreements, and concludes with a commentary on different strategies proposed to ensure that health is not compromised by trade liberalization treaties.