Molecular Insights into Carbon Dioxide Sorption in Hydrazone-Based Covalent Organic Frameworks with Tertiary Amine Moieties

Tailorable sorption properties at the molecular level are key for efficient carbon capture and storage and a hallmark of covalent organic frameworks (COFs). Although amine functional groups are known to facilitate CO2 uptake, atomistic insights into CO2 sorption by COFs modified with amine-bearing functional groups are scarce. Herein, we present a detailed study of the interactions of carbon dioxide and water with two isostructural hydrazone-linked COFs with different polarities based on the 2,5-diethoxyterephthalohydrazide linker. Varying amounts of tertiary amines were introduced in the COF backbones by means of a copolymerization approach using 2,5-bis(2-(dimethylamino)ethoxy)terephthalohydrazide in different amounts ranging from 25 to 100% substitution of the original DETH linker. The interactions of the frameworks with CO2 and H2O were comprehensively studied by means of sorption analysis, solid-state NMR spectroscopy, and quantum-chemical calculations. We show that the addition of the tertiary amine linker increases the overall CO2 sorption capacity normalized by the surface area and of the heat of adsorption, whereas surface areas and pore size diameters decrease. The formation of ammonium bicarbonate species in the COF pores is shown to occur, revealing the contributing role of water for CO2 uptake by amine-modified porous frameworks

Scaling analyses for hyperpolarization transfer across a spin-diffusion barrier and into bulk solid media

By analogy to heat and mass transfer film theory, a general approach is introduced for determining hyperpolarization transfer rates between dilute electron spins and a surrounding nuclear ensemble. These analyses provide new quantitative relationships for understanding, predicting, and optimizing the effectiveness of hyperpolarization protocols, such as Dynamic Nuclear Polarization (DNP) under magic-angle spinning conditions. An empirical DNP polarization-transfer coefficient is measured as a function of the bulk matrix H-1 spin density and indicates the presence of two distinct kinetic regimes associated with different rate-limiting polarization transfer phenomena. Dimensional property relationships are derived and used to evaluate the competitive rates of spin polarization generation, propagation, and dissipation that govern hyperpolarization transfer between large coupled spin ensembles. The quantitative analyses agree closely with experimental measurements for the accumulation, propagation, and dissipation of hyperpolarization in solids and provide evidence for kinetically-limited transfer associated with a spin-diffusion barrier. The results and classical approach yield general design criteria for analyzing and optimizing polarization transfer processes involving complex interfaces and composite media for applications in materials science, physical chemistry and nuclear spintronics

Measurement of Proton Spin Diffusivity in Hydrated Cementitious Solids

The study of hydration and crystallization processes involving inorganic oxides is often complicated by poor long-range order and the formation of heterogeneous domains or surface layers. In solid-state NMR, H-1-H-1 spin diffusion analyses can provide information on spatial composition distributions, domain sizes, or miscibility in both ordered and disordered solids. Such analyses have been implemented in organic solids but crucially rely on separate measurements of the 1 H-1 spin diffusion coefficients in closely related systems. We demonstrate that an experimental NMR method, in which "holes" of well-defined dimensions are created in proton magnetization, can be applied to determine spin diffusion coefficients in cementitious solids hydrated with O-17-enriched water. We determine proton spin diffusion coefficients of 240 +/- 40 nm(2)/s for hydrated tricalcium aluminate and 140 +/- 20 nm(2)/s for hydrated tricalcium silicate under quasistatic conditions

A Photochemical Approach to Directing Flow and Stabilizing Topography in Polymer Films

Coatings and substrates with topographically patterned features will play an important role in efficient technologies for harvesting and transmitting light energy. In order to address these applications, a methodology for prescribing height profiles in polymer films is presented here. This is accomplished by photochemcially patterning a solid-state, sensitized polymer film. After heating the film above its glass transition temperature, melt-state flow is triggered and directed by the chemical pattern. A second light exposure was applied to fully activate a heat-stable photo-crosslinking additive. The features formed here are thermochemically stable and can act as an underlayer in a multilayered film. To exemplify this capability, these films were also used to direct the macroscopic film morphology of a block copolymer overlayer

Prevalence of peripheral artery disease by abnormal ankle-brachial index in atrial fibrillation: implications for risk and therapy.

To the Editor: Nonvalvular atrial fibrillation (NVAF) is the most common sustained arrhythmia encountered in clinical practice and is associated with a 5-fold increased risk for stroke (1). Moreover, patients with NVAF often suffer from atherosclerotic complications such as acute myocardial infarction (AMI) (2). Peripheral artery disease (PAD) is an established marker of systemic atherosclerosis but its prevalence in NVAF is still unclear. We reasoned that inclusion of ankle-brachial index (ABI), which is an established tool for diagnosis of PAD (3), in the CHA2DS2-VASc (4) score would better define the prevalence of vascular disease. To address this issue, the Italian Society of Internal Medicine (SIMI) established an Italian registry documenting ABI in NVAF patients. The Atrial Fibrillation Registry for the ARAPACIS (Ankle-brachial Index Prevalence Assessment: Collaborative Italian Study) study is an independent research project involving all Regional Councils of SIMI. The first objective of the study was to estimate the prevalence of ABI 640.90 in NVAF patients. Consecutive patients with NVAF referred to internal medicine wards were eligible for the enrollment. Enrollment started in October 2010 and continued until October 30, 2012. Patients were enrolled if they were 18 years or older and had a diagnosis of NVAF, recording during the qualifying admission/consultation or in the preceding 12 months, and if it was possible to obtain the ABI measurement. Exclusion criteria included the following: acquired or congenital valvular AF, active cancer, disease with life expectancy <3 years, hyperthyroidism and pregnancy. We initially planned to include 3,000 patients. The Data and Safety Monitoring Board (Online Appendix) decided to perform an interim analysis to assess the prevalence of ABI in the enrolled populations\u2014as a higher than expected prevalence of low ABI was detected\u2014and decided to interrupt the patients' enrollment. The sample size was amended as follows: a sample of 2,027 patients leads to the expected prevalence of 21% with a 95% confidence interval width of 3.5% (StataCorp LP, College Station, Texas). Among the 2,027 NVAF patients included in the study, hypertension was detected in 83%, diabetes mellitus in 23%, dyslipidemia in 39%, metabolic syndrome in 29%, and smoking in 15%. At least 1 atherosclerotic risk factor was detected in 90% of patients. The NVAF population was at high risk for stroke, with only 18% having a CHA2DS2-VASc score of 0 to 1, while 82% had a risk 652. Despite this, 16% were untreated with any antithrombotic drug, 19% were treated with antiplatelet drugs (APs), and 61% with oral anticoagulants (OAC); 4% of patients were treated with both APs and OAC. Among the AF population, 428 patients (21%) had ABI 640.90 compared with 1,381 patients, who had an ABI of 0.91 to 1.39 (69%); 204 patients (10%) had ABI 651.40 (Fig. 1). ABI recorded only in 1 leg was excluded from the analysis (n = 14). ABI 640.90 progressively increased from paroxysmal to permanent NVAF (18%, 21%, 24%; p = 0.0315). Figure 1. ABI Distribution of Any Category and CHA2DS2-VASc Score Including ABI 640.90 C = congestive heart failure (or left ventricular systolic dysfunction) (Points: 1), H = hypertension (Points: 1), A2 = Age 6575 years (Points: 2), D = diabetes mellitus (Points: 1), S2 = prior stroke or transient ischemic attack or thromboembolism (Points: 2); V = vascular disease (previous acute myocardial infarction, peripheral arterial disease, or aortic plaque) (Points: 1); A = age 65 to 74 years (Points: 1); Sc = sex category (female) (Points: 1). ABI = ankle brachial index. Figure optionsDownload full-size imageDownload high-quality image (447 K)Download as PowerPoint slide NVAF patients with ABI 640.90 were more likely to be hypertensive (88% vs. 82%; p = 0.032), diabetic (34% vs. 20%; p 0.90 (93% vs. 82%; p < 0.0001). Logistic regression analysis demonstrated that ABI 640.90 was significantly associated with a smoking habit (odds ratio [OR]: 1.99; 95% confidence interval [CI]: 1.48 to 2.66; p < 0.0001), diabetes (OR: 1.93; 95% CI: 1.51 to 2.46; p < 0.0001), age class 65 to 74 years (OR: 2.05; 95% CI: 1.40 to 3.07; p < 0.0001), age class 6575 years (OR: 3.12; 95% CI: 2.16 to 4.61; p < 0.0001), and history of previous transient ischemic attack/stroke (OR: 1.64; 95% CI: 1.20 to 2.24; p = 0.002). Vascular disease, as assessed by the history elements of CHA2DS2VASc score, was recorded in 17.3% of patients; inclusion of ABI 640.90 in the definition of vascular disease yielded a total prevalence of 33%. A higher prevalence of vascular disease was detected if ABI 640.90 was included in the CHA2DS2VASc score (Fig. 1). CHA2DS2VASc including ABI 640.90 was more associated with previous stroke (43%; OR: 1.85; 95% CI: 1.41 to 2.44; p < 0.0001) compared to CHA2DS2VASc with ABI 0.91 to 1.39 (23%; OR: 1.52; 95% CI: 1.10 to 2.11; p = 0.0117). To the best of our knowledge, there is no large-scale study that specifically examined the prevalence of ABI 640.90 in NVAF. In our population, 21% had ABI 640.90 indicating that NVAF is often associated with systemic atherosclerosis. The CHADS2 has been recently refined with the CHA2DS2-VASc score, which includes vascular disease as documented by a history of AMI, symptomatic PAD, or detection of atherosclerotic plaque in the aortic arch (4). Comparison of vascular prevalence as assessed by CHA2DS2-VASc score and/or ABI 640.90 is of interest to define the potentially positive impact of measuring ABI in the management of NVAF patients. Inclusion of ABI 640.90 in the definition of vascular disease greatly increased the prevalence of vascular disease, which increased from 17.3% (based on history alone) to 33% (based on ABI) in the entire population. If ABI 640.90 was encompassed in the definition of vascular disease of CHA2DS2-VASc score the prevalence of vascular disease increased in every risk class. Inclusion of ABI 640.90 in the CHA2DS2-VASc score allowed us to better define the risk profile of NVAF patients with an up-grading of the risk score in each CHA2DS2-VASc score category. This may have important therapeutic implications if the new score could be tested prospectively, as a higher number of NVAF patients would potentially be candidates for an anticoagulant treatment by measuring ABI. A prospective study is, therefore, necessary to validate the risk score of this new definition of vascular disease. In conclusion, this study provides the first evidence that one-fifth of NVAF patients had an ABI 640.90, indicating that it may represent a simple and cheap method to better define the prevalence of vascular disease in NVAF

Prevalence of peripheral artery disease by abnormal ankle-brachial index in atrial fibrillation: Implications for risk and therapy

To the Editor: Nonvalvular atrial fibrillation (NVAF) is the most common sustained arrhythmia encountered in clinical practice and is associated with a 5-fold increased risk for stroke (1). Moreover, patients with NVAF often suffer from atherosclerotic complications such as acute myocardial infarction (AMI) (2). Peripheral artery disease (PAD) is an established marker of systemic atherosclerosis but its prevalence in NVAF is still unclear. We reasoned that inclusion of ankle-brachial index (ABI), which is an established tool for diagnosis of PAD (3), in the CHA2DS2-VASc (4) score would better define the prevalence of vascular disease. Toaddress this issue, the ItalianSociety of InternalMedicine (SIMI) established an Italian registry documenting ABI inNVAF patients. The Atrial Fibrillation Registry for the ARAPACIS (Ankle- brachial Index Prevalence Assessment: Collaborative Italian Study) study is an independent research project involving all Regional Councils of SIMI. The first objective of the study was to estimate the prevalence of ABI 0.90 in NVAF patients. Consecutive patients with NVAF referred to internal medicine wards were eligible for the enrollment. Enrollment started in October 2010 and continued until October 30, 2012. Patients were enrolled if they were 18 years or older and had a diagnosis of NVAF, recording during the qualifying admission/consultation or in the preceding 12 months, and if it was possible to obtain the ABI measurement. Exclusion criteria included the following: acquired or congenital valvular AF, active cancer, disease with life expectancy &lt;3 years, hyperthyroidism and pregnancy. We initially planned to include 3,000 patients. The Data and Safety Monitoring Board (Online Appendix) decided to perform an interim analysis to assess the prevalence of ABI in the enrolled populationsdas a higher than expected prevalence of low ABI was detecteddand decided to interrupt the patients’ enrollment. The sample size was amended as follows: a sample of 2,027 patients leads to the expected prevalence of 21% with a 95% confidence interval width of 3.5% (StataCorp LP, College Station, Texas). Among the 2,027 NVAF patients included in the study, hyper- tension was detected in 83%, diabetes mellitus in 23%, dyslipidemia in 39%, metabolic syndrome in 29%, and smoking in 15%. At least 1 atherosclerotic risk factor was detected in 90% of patients. The NVAF population was at high risk for stroke, with only 18% having a CHA2DS2-VASc score of 0 to 1, while 82% had a risk 2. Despite this, 16% were untreated with any antith- rombotic drug, 19% were treated with antiplatelet drugs (APs), and 61% with oral anticoagulants (OAC); 4% of patients were treated with both APs and OAC. Among the AF population, 428 patients (21%) had ABI 0.90 (69%); 204 patients (10%) had ABI 1.40 (Fig. 1). ABI recorded only in 1 leg was excluded from the analysis (n ¼ 14). ABI 0.90 progressively increased from paroxysmal to permanent NVAF (18%, tensive (88% vs. 82%; p ¼ 0.032), diabetic (34% vs. 20%; p &lt; 0.0001), or smokers (20% vs. 14%; p ¼ 0.0008), or to have experi- enced transient ischemic attack or stroke (17% vs. 10%; p &lt; 0.001). 21%, 24%; p ¼ 0.0315). NVAF patients with ABI 0.90 were more likely to be hyper- NVAF patients with ABI 0.90 had a higher percentage of CHA2DS2-VASc score 2 compared with those with ABI &gt;0.90 (93% vs. 82%; p &lt; 0.0001). significantly associated with a smoking habit (odds ratio [OR]: 1.99; 95% confidence interval [CI]: 1.48 to 2.66; p &lt; 0.0001), diabetes (OR: 1.93; 95% CI: 1.51 to 2.46; p &lt; 0.0001), age class 65 to 74 years (OR: 2.05; 95% CI: 1.40 to 3.07; p &lt; 0.0001), age Logistic regression analysis demonstrated that ABI 0.90 was class 75 years (OR: 3.12; 95% CI: 2.16 to 4.61; p &lt; 0.0001), and history of previous transient ischemic attack/stroke (OR: 1.64; 95% CI: 1.20 to 2.24; p ¼ 0.002). Vascular disease, as assessed by the history elements of CHA2DS2VASc score, was recorded in 17.3% of patients; inclu- sion of ABI 0.90 in the definition of vascular disease yielded a total prevalence of 33%. A higher prevalence of vascular disease was detected if ABI 0.90 was included in the CHA2DS2VASc score (Fig. 1). CHA2DS2VASc including ABI 0.90 was more associated with previous stroke (43%; OR: 1.85; 95% CI: 1.41 to 2.44; p &lt; 0.0001) compared to CHA2DS2VASc with ABI 0.91 to 1.39 (23%; OR: 1.52; 95% CI: 1.10 to 2.11; p ¼ 0.0117). To the best of our knowledge, there is no large-scale study that specifically examined the prevalence of ABI 0.90 in NVAF. In our population, 21% had ABI 0.90 indicating that NVAF is often associated with systemic atherosclerosis. The CHADS2 has been recently refined with the CHA2DS2- VASc score, which includes vascular disease as documented by a history of AMI, symptomatic PAD, or detection of atheroscle- rotic plaque in the aortic arch (4). Comparison of vascular prevalence as assessed by CHA2DS2- NVAF patients. Inclusion of ABI 0.90 in the definition of vascular disease greatly increased the prevalence of vascular disease, which increased from 17.3% (based on history alone) to 33% (based compared with 1,381 patients, who had an ABI of 0.91 to 1.39 to better define the risk profile ofNVAFpatients with an up-grading of the risk score in each CHA2DS2-VASc score category. This may have important therapeutic implications if the new score could be tested prospectively, as a higher number of NVAF patients would on ABI) in the entire population. If ABI 0.90 was encompassed in the definition of vascular disease of CHA2DS2-VASc score the prevalence of vascular disease increased in every risk class. Inclusion of ABI0.90 in theCHA2DS2-VASc score allowed us VASc score and/or ABI 0.90 is of interest to define the poten- tially positive impact of measuring ABI in the management of potentially be candidates for an anticoagulant treatment by measuring ABI. A prospective study is, therefore, necessary to validate the risk score of this new definition of vascular disease. In conclusion, this study provides the first evidence that one-fifth of NVAF patients had an ABI 0.90, indicating that it may represent a simple and cheap method to better define the prevalence of vascular disease in NVAF