bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hemodynamic assessment in heart failure
Authors: Jain Christopher Charles , Borlaug Barry A. 
Published: September 2019

AbstractHemodynamics play a central role in the pathophysiology of heart failure (HF), yet their proper assessment and optimization remains challenging. Heart failure is defined as the inability of the heart to deliver adequate perfusion (cardiac output) to the body at rest or exercise, or to require an elevation in cardiac filling pressures in order to do this. This bedrock definition is important because it relies on measurable quantities (filling pressures and output) that are readily assessed in the cardiac catheterization laboratory. Here we present three cases to illustrate how better understanding of the determinants of cardiac output and stroke volume: preload, afterload, contractility, and lusitropy, as well as the determinants of congestion (high filling pressures) may be used to guide optimization of hemodynamic status. The goal is that the readers will be able to think more critically when evaluating the hemodynamics of their patient in HF and recognize the complex interplay that determines the complex balance between cardiac ejection and filling capabilities, and how this alters symptoms and outcomes for patients with HF.Key Points
Careful assessment of hemodynamics in the catheterization laboratory allows for actionable insight to a patient's volume status, cardiac function and can help prognosticate outcomes.
Exercise hemodynamics in heart failure is a powerful tool to better understand the cause of symptoms and predict outcomes.
Clinicians should aim to decrease biventricular filling pressures to normal values to improve morbidity and reduce risk for readmission.
In patients with heart failure and reduced ejection fraction, clinicians should aim to decrease afterload as much as can be tolerated by the renal function and patient's symptoms.
Low cardiac output can often be improved by optimizing preload and afterload rather than initiating inotropes, which should be reserved until needed.
In advanced heart failure, the right heart function becomes a key determinant of symptoms and outcomes.
Fast Cyclohexane Oxidation Under Mild Reaction Conditions Through a Controlled Creation of Redox‐Active Fe(II/III) Sites in a Metal−Organic Framework
Authors: Kim Ah‐Reum , Ahn Sol , Yoon Tae‐Ung , Notestein Justin M. , Farha Omar K. , Bae Youn‐Sang 
Published: September 2019

AbstractMIL‐100(Fe), a metal−organic framework containing coordinatively unsaturated iron sites, was prepared by a solvothermal method and utilized in cyclohexane oxidation. Interestingly, the composition and fraction of redox‐active Fe(II/III) sites in MIL‐100(Fe) could be tuned by using different pretreatment temperatures. The obtained materials were characterized by means of field‐emission scanning electron microscopy (FE‐SEM), powder X‐ray diffraction (PXRD), N2 adsorption‐desorption isotherms, and X‐ray photoelectron spectroscopy (XPS). Due to the presence of redox‐active coordinatively unsaturated sites (CUS) at the iron atoms, MIL‐100(Fe) exhibited good performance for cyclohexane oxidation under mild reaction conditions. Oxidation rates were significantly enhanced when reduced FeII sites were generated by high‐temperature pretreatments. In either high‐temperature or low‐temperature pretreatment, the isolated Fe(II/III) sites in MIL‐100 were far more reactive in cyclohexane oxidation than were bulk iron oxide materials. Finally, possible reaction pathways were proposed based on radical, Haber‐Weiss routes.
Iridium Water Oxidation Catalysts Based on Pyridine‐Carbene Alkyl‐Substituted Ligands
Authors: Corbucci Ilaria , Zaccaria Francesco , Heath Rachel , Gatto Giordano , Zuccaccia Cristiano , Albrecht Martin , Macchioni Alceo 
Published: September 2019

AbstractIridium complexes bearing pyridine triazolylidene ligands with variable steric hindrance, derived by the presence of an R group (R=H, Me, Et, nPr, iPr, Bu, and Oct) onto the N1‐nitrogen, have been synthesized, fully characterized and tested as water oxidation catalysts (WOCs), using chemical sacrificial oxidants (CAN and NaIO4) or in photocatalytic experiments ([Ru(bpy)3]Cl2 as phosensitizer and Na2S2O8 as an electron acceptor). The catalytic activity is barely affected by the nature of R when WO is driven by NaIO4 (1 min−1<TOF<14 min−1) or light/[Ru(bpy)3]Cl2/Na2S2O8 (TOF≈0.15 min−1); on the contrary, a remarkable effect is observed with CAN. Particularly, in the latter case, complexes with R=H and Me exhibit similar activity (10 min−1<TOF<20 min−1), whereas all other complexes (R=Et, Pr, i‐Pr, Bu, and Oct) are significantly more active and exhibit comparable TOFs in the range 40–130 min−1. Thus, a marked discontinuity in performances occurs when passing from R=Me to R=Et. This can be hardly explained solely based on the previously proposed hypothesis, suggesting that an increased R‐dimension might favor the association of iridium complexes leading to the formation of highly active multimetallic species. An additional, more specific effect has to be present. It appears plausible that the steric hindrance introduced in close proximity of the iridium center, when R≥Et, hampers transfer of the hydroperoxo or peroxo moiety from iridium active species to cerium, a process that could slow down kinetics of O2 evolution.
Manganese‐Catalyzed Transfer Hydrogenation of Nitriles with 2‐Butanol as the Hydrogen Source
Authors: Garduño Jorge A. , Flores‐Alamo Marcos , García Juventino J. 
Published: September 2019

AbstractWe report herein the first example of a homogeneous manganese catalyzed transfer hydrogenation of nitriles using 2‐BuOH as the hydrogen source. Compound fac‐[(CO)3Mn{iPr2P(CH2)2PiPr2}Br] (Mn‐1, 3 mol %) exhibited catalytic activity in the presence of KOtBu (10 mol %) for the transfer hydrogenation of benzonitrile to yield a mixture of benzylamine (BA) and N‐sec‐butylidenebenzylamine (SBA). Subsequent acidic hydrolysis yielded isolated benzylamine hydrochloride in 96 %. The title system featured reversible formation of N‐benzylidenebenzylamine (BBA) prior to formation of SBA. A series of amine hydrochlorides was prepared following this methodology (39–92 % isolated yields, 4 examples). Best substrates for this transformation are electron‐rich aromatic nitriles, nonetheless electron‐deficient aromatic as well as aliphatic nitriles were also hydrogenated. Mechanistic studies suggested coordinatively unsaturated Mn‐hydride species performing catalytic turnover.
Effect of the sp3/sp2 Ratio in Boron‐Doped Diamond Electrodes on the Degradation Pathway of Aniline by Anodic Oxidation
Authors: Espinoza L. Carolina , Aranda Mario , Contreras David , Henríquez Adolfo , Salazar Ricardo 
Published: September 2019

AbstractThe sp3/sp2 ratio present in boron‐doped diamond (BDD) electrodes conditions the way in which organic compounds are oxidized and transformed to CO2 during anodic oxidation. A higher content of sp3 carbon on the surface favors the generation of hydroxyl radicals over the oxygen evolution reaction, which generates different degradation byproducts. In this work, we studied the degradation of aniline by anodic oxidation using five BDD electrodes with different sp3/sp2 ratios in sulfate and chloride media. Aniline was degraded using the five BDD electrodes in both electrolytes, and clear differences were observed in the intermediates produced during the electrolysis. BDD electrodes with higher sp3 proportions allowed for greater degradation and mineralization of aniline with lower molecular weight and the production of fewer toxic organic byproducts. Degradation pathways for aniline in sulfate and chloride media are proposed, evidencing the differences in the oxidation mechanisms for aniline and its byproducts due to the varying sp3/sp2 ratio in the BDD electrodes.
Star‐Shaped Gold Nanoparticles as Friendly Interfaces for Protein Electrochemistry: the Case Study of Cytochrome c
Authors: Silveira Célia M. , Zumpano Rosaceleste , Moreira Miguel , de Almeida Miguel Peixoto , Oliveira Maria João , Bento Marina , Montez Cláudia , Paixão Inês , Franco Ricardo , Pereira Eulália , Almeida M. Gabriela 
Published: September 2019

AbstractGold nanostars with an average tip‐to‐tip length of 52±6 nm were functionalized with different capping agents and used as electrode modification materials for protein electrochemistry. Direct electron transfer between cytochrome c and nanostar‐coated pyrolytic graphite electrodes was observed with the protein in solution. The electrochemical response was improved at nanostars functionalized with a 1 : 1 mixture of 11‐mercaptoundecanoic acid and 4‐mercaptobenzoic acid in comparison with gold nanospheres coated with a similar functionalization. Further immobilization of cytochrome c on pyrolytic graphite while conjugated with the same nanostars guaranteed the maintenance of the protein's native properties, whereas direct adsorption on the bare or nanostar‐modified electrodes resulted in an altered conformational state. The pseudo‐peroxidase activity of the altered cytochrome c was enhanced in the presence of the nanostars.
Unexpectedly Large Couplings Between Orthogonal Units in Anthraquinone Polymers
Authors: Fornari Rocco P. , de Silva Piotr 
Published: September 2019

AbstractThe unusual electronic properties of directly linked 1,4‐polyanthraquinones (14PAQs) are investigated. The dihedral angle between the molecular planes of anthraquinones (AQs) is found to be close to 90°. Contrary to the prevailing notion that the interaction between orthogonal units is negligible due to broken π‐electron conjugation, the coupling between neighboring AQ units does not have a minimum at 90° and is much larger than that expected. The unexpectedly large electronic coupling between orthogonal AQ units is explained by the interaction between the lone pairs of the carbonyl oxygen and the π system of the neighboring unit, which allows favorable overlap between frontier molecular orbitals at the orthogonal geometry. It is shown that this effect, which is described computationally for the first time, can be strengthened by adding more quinone units. The effect of thermal fluctuations on the couplings is assessed through ab initio molecular dynamics simulations. The distributions of the couplings reveal that electron transport is resilient to dynamic disorder in all systems considered, whereas the hole couplings are much more sensitive to disorder. Lone pair–π interactions are described, as a previously largely overlooked conjugation mechanism, for incorporation into a new class of disorder‐resilient semiconducting redox polymers.
Dearomatization of 3‐Nitroindoles with Highly γ‐Functionalized Allenoates in Formal (3+2) Cycloadditions
Authors: Birbaum Léo , Gillard Laurent , Gérard Hélène , Oulyadi Hassan , Vincent Guillaume , Moreau Xavier , De Paolis Michael , Chataigner Isabelle 
Published: September 2019

Abstract3‐Nitroindoles are easily reacted with highly substituted γ‐allenoates in the presence of a commercially available phosphine catalyst. For instance, allenoates derived from biomolecules such as amino and deoxycholic acids are combined for the first time with 3‐nitroindole. The corresponding dearomatized (3+2) tricyclic cycloadducts are obtained as α‐regioisomers exclusively. DFT computations shed light on this multi‐step reaction mechanism and on the selectivities observed in the sequence.
Highly Efficient Multiple‐Labeling Probes for the Visualization of Enzyme Activities
Authors: Song Heng , Li Yuyao , Chen Yefeng , Xue Chenghong , Xie Hexin 
Published: September 2019

AbstractQuinone methide (QM) as a latent trapping unit has been widely explored in activity‐based self‐immobilizing reagents. However, further application of this strategy has been largely hampered by the limited labeling efficiency to proteins. In this study, a thorough investigation on the labeling efficiency and the structure of QM‐based trapping unit is presented, from which a QM with multiple leaving groups was identified as an optimal trapping unit. An alkaline phosphatase (ALP) immobilizing reagent featured with this multiple‐labeling trapping unit exhibited lower nonspecific binding and, remarkably, a significantly higher labeling efficiency over other immobilizing reagents upon enzymatic activation. The utility of this imaging reagent was further demonstrated with the in vitro and in vivo visualization of the ALP activities. Furthermore, the multiple functional trapping unit may find greater value in the other activity‐based immobilizing probes.
Controlled Heterometallic Composition in Linear Trinuclear [LnCeLn] Lanthanide Molecular Assemblies
Authors: Velasco Verónica , Barrios Leoní A. , Schütze Mike , Roubeau Olivier , Luis Fernando , Teat Simon J. , Aguilà David , Aromí Guillem 
Published: September 2019

AbstractThe combination of two different β‐diketone ligands facilitates the size‐controlled assembly of pure heterometallic [LnLn′Ln] linear compounds thanks to two different coordination sites present in the molecular scaffold. [HoCeHo], [ErCeEr], and [YbCeYb] analogues are presented here and are characterized both in the solid state and in solution, demonstrating the selectivity of this unique method to produce heterometallic 4f molecular entities.
Facile SILAR Processed Bi2S3:PbS Solid Solution on MWCNTs for High‐performance Electrochemical Supercapacitor
Authors: Pandit Bidhan , Pande Shilpa A. , Sankapal Babasaheb R. 
Published: September 2019

Summary of main observation and conclusionCarbon based composite materials have gained much attention because of fulfilling desirable properties for supercapacitor application. In the featured work, the thin film of Bi2S3:PbS solid solution has been synthesized on multi‐walled carbon nanotubes (MWCNTs) by simple successive ionic layer adsorption and reaction (SILAR) method. The nanoparticle morphology provides sufficient electroactive channels for electrolyte ions to penetrate during electrochemical activities. The composite exhibits superior specific capacitance 676 F/g at constant specific current density of 5.56 A/g with fast charge‐discharge cycles. In association of energy storage characteristics, the fabricated symmetric cell exhibits excellent energy density of 13.36 Wh/kg by acquiring power density of 0.83 kW/kg. The superior results of the hybrid electrode promise a novel direction for high performance supercapacitor application.
Risk and subtypes of secondary primary malignancies in diffuse large B‐cell lymphoma survivors change over time based on stage at diagnosis
Authors: Major Ajay , Smith Derek E. , Ghosh Debashis , Rabinovitch Rachel , Kamdar Manali 
Published: September 2019

BackgroundPrevious studies have shown an increased risk of secondary primary malignancies (SPMs) after diffuse large B‐cell lymphoma (DLBCL) treatment. Whether stage of DLBCL at diagnosis affects the subtypes of SPMs that occur has not been previously described.MethodsThe Surveillance, Epidemiology, and End Results database was queried for patients aged >18 years diagnosed with primary DLBCL from 1973 to 2010 and categorized by early stage (ES) (stage I‐II) or advanced stage (AS) (stage III‐IV) disease. Differences in overall and location‐specific SPM incidence by stage and time since diagnosis were assessed in 5‐year intervals using a Fine‐Gray hazards model. Overall survival was compared using the log‐rank test. A Cox proportional hazards model was used to assess differences in survival.ResultsIn total, 26,038 patients with DLBCL were identified, including 14,724 with ES and 11,314 with AS disease. The median follow‐up was 13.3 years. Overall, 13.0% of patients developed SPM, with a higher but nonsignificantly increased risk of SPM development in those who had ES disease compared with those who had AS disease (14% vs 11.6%; P = .14). During the first 5 years after diagnosis, patients who had ES disease had a higher risk of SPM than those who had AS disease, specifically colorectal, pancreas, breast, and prostate SPMs. During the period from 10 to 15 years after diagnosis, patients who had AS disease had a higher risk of SPM than those who had ES disease, specifically hematologic SPMs. Development of SPM was found to significantly increase the risk of death regardless of stage at diagnosis.ConclusionsIn this large, population‐based study, distinctly different subtypes and temporal patterns of SPM development were identified based on stage of DLBCL at diagnosis. The current study merits consideration of tailored site‐specific and time‐specific surveillance for patients with DLBCL according to stage and time interval since diagnosis.
Concomitant Polymorphism in an Organic Solid: Molecular and Crystal Structure and Intra‐ and Intermolecular Potential Contributions to tert‐Butyl and Methyl Group Rotation
Authors: Beckmann Peter A. , Rablen Paul R. , Schmink Jason , Szewczyk Steven T. , Rheingold Arnold L. 
Published: September 2019

AbstractWe investigate the relationship between structure (crystal and molecular) and tert‐butyl and methyl group dynamics in 2‐(tert‐butyl)‐9‐(4‐(tert‐butyl)phenyl)anthracene. Powder and single‐crystal X‐ray diffraction, taken together, show that different polycrystalline samples recrystallized from different solvents have different amounts of at least four polymorphs (crystallites having different crystal structures), of which we have identified three by single crystal X‐ray diffraction. The molecules in the asymmetric units of the different crystal structures differ by the dihedral angle the tert‐butylphenyl group makes with the anthracene moiety. Ab initio electronic structure calculations on the isolated molecule show that very little intramolecular energy is required to change this angle over a range of about 60° which is probably the origin of the concomitant polymorphism (crystals of more than one polymorph in a polycrystalline sample). Solid state 1H nuclear magnetic resonance (NMR) spin‐lattice relaxation experiments support the powder and single‐crystal X‐ray results and provide average NMR activation energies (closely related to rotational barriers) for the rotation of the tert‐butyl groups and their constituent methyl groups. These barriers have both an intramolecular and an intermolecular component. The latter is sensitive to the crystal structure. The intramolecular components of the rotational barriers of the two tert‐butyl groups in the isolated molecule are investigated with ab initio electronic structure calculations.
Endothelial dysfunction and cardiovascular outcome in asymptomatic patients with type 2 diabetes: A pilot study
Authors: Villano Angelo , Mencarelli Erica , Melita Veronica , Rizzi Alessandro , Lamendola Priscilla , De Vita Antonio , Manfredonia Laura , Ravenna Salvatore Emanuele , Pitocco Dario , Lanza Gaetano Antonio , Crea Filippo 
Published: September 2019

AbstractBackgroundType 2 diabetes mellitus (T2DM) is associated with an increased risk of cardiovascular events, but risk stratification of asymptomatic T2DM patients remains a challenging issue. We conducted a pilot study to assess whether endothelial dysfunction might help identify, among asymptomatic T2DM patients, those at increased risk of cardiovascular events.MethodsWe studied 61 consecutive T2DM patients with no evidence of cardiovascular disease and no insulin therapy. Endothelial function was assessed by flow‐mediated dilation (FMD) of the right brachial artery. The primary endpoint was a combination of major cardiovascular events (MACE: cardiovascular death, acute coronary events, coronary interventions, and acute cerebrovascular accidents). FMD was repeated at follow‐up in 48 patients (79%).ResultsA total of 10 MACE (16.4%) occurred during a mean follow‐up of 48 months, including three acute myocardial infarctions, five coronary revascularizations for stable angina, and two acute ischaemic strokes. FMD at enrolment was lower in patients with compared with patients without MACE (3.78 ± 0.97% vs 4.70 ± 1.33%, respectively; P = .04). No other clinical or laboratory variables (age, diabetes duration, glycated haemoglobin, cardiovascular risk factors, drug therapy, and nitrate‐mediated dilation) were associated with MACE. FMD at follow‐up was also lower in patients with (n = 10) compared with those without (n = 38) MACE (3.66 ± 1.29 vs 4.85 ± 1.92; P = .006).ConclusionsOur data suggest that assessment of FMD might be helpful to identify patients at increased risk of MACE among individuals with asymptomatic T2DM; accordingly, a large study is warranted to adequately define the clinical utility of FMD assessment in the management of T2DM patients.
Moderators and mediators of outcome in treatments for anorexia nervosa and bulimia nervosa in adolescents: A systematic review of randomized controlled trials
Authors: Hamadi Layla , Holliday Joanna 
Published: September 2019

AbstractObjectiveTo critically appraise papers reporting on moderators and mediators of recommended psychological treatments for anorexia nervosa (AN) and bulimia nervosa (BN) in adolescents.MethodA systematic search of databases was conducted including PsycINFO, Embase, MEDLINE, AMED, CINAHL, and the Cochrane Library. Studies were included where a randomized controlled trial (RCT) compared therapies for AN or BN and reported on moderators or mediators of treatment effect. Twenty‐one eligible papers were included, all based on data from eight RCTs.ResultsFamily therapies were dominant in the literature. Individual or separated treatment appeared superior for families with more difficult relationships, whereas conjoint family treatment appeared to be superior where good family relationships were reported. Where there was greater eating disorder psychopathology in AN, including eating disorder‐related obsessions and compulsions, the response was better to a family approach than to individual therapies. There was some evidence that a family treatment was superior for those engaging in purging behaviors in BN. Measures of family relationships, parental self‐efficacy, and early change emerged as possible mediators; however, the quality of evidence was mixed and the findings, in some cases, arguably circular. Moderator and mediator analyses were underpowered in all studies, with multiple, and post‐hoc, analyses being run, and a broad range of outcome measures used.DiscussionThis review recommends that emerging findings are explored further in adequately powered trials of the different recommended therapies, with a move toward focusing on effect sizes. A consensus on acceptable definitions of outcome, including remission and recovery, would benefit future research.
Reduction of sixth‐order radial force by harmonic current control and its application to EPS motors
Authors: Watahiki Masanori , Mori Tomonari , Lan Linfeng , Tanaka Junya , Ueda Tomoya , Fukumura Tomohiro , Kanematsu Masato , Fujimoto Hiroshi 
Published: September 2019

AbstractTo improve noise and vibration of Electric Power Steering (EPS) system, we focus on the reduction of the sixth‐order radial force of an EPS motor by regulating its harmonic current. Because an EPS system is operated in a wide speed range, a reduction method is required to work even for dynamic motor speed. In this article, we introduce our method and report its test result to show the reduction of sixth‐order radial vibration of an EPS motor.