bluuebunny/crossref_metadata_2025 huggingface dataset:
Multi‐Component Metal‐Organic Frameworks Significantly Boost Visible‐Light‐Driven Hydrogen Production Coupled with Selective Organic Oxidation
Authors: Li Hanning , Yang Yang , Jing Xu , He Cheng , Duan Chunying
Published: March 2021

Visible‐light‐driven hydrogen production coupled with selective organic oxidation has attracted increasing attention, as it not only provides clean and renewable energy, but also utilizes the other half reaction to achieve some value‐added organic chemicals. Metal‐organic frameworks based on metal clusters and organic ligands self‐assembly give a perspective on the formation of multifunctional heterogeneous photocatalyst to significantly boost visible‐light photocatalytic activities under mild conditions. By incorporating two types of photoactive units, tricarboxytriphenylamine (H3TCA) and tris(4‐(pyridinyl)phenyl)amine (NPy3), into a single metal‐organic frameworks, a multi‐component MOF Co‐MIX was obtained. With the redox active metal centers enabling the photoexcitation reduction of protons into hydrogen and the photogenerated holes promoting considerable oxidation of substrates, the resulting Co‐MIX exhibits high catalytic activity for the photocatalytic hydrogen production coupled with selective oxidation of benzylamine or 1,2,3,4‐tetrahydroisoquinoline. Importantly, the photocatalytic experiments of single‐component Co‐TCA and Co‐NPy3 verified the positive synergistic effects on stability and photocatalytic ability of the two ligands (H3TCA and NPy3) in one single MOF, revealing that the multi‐component strategy is very important for the efficient charge separation and excellent photocatalytic activity of the catalyst.
Narrative expectations in financial forecasting
Authors: Johnson Samuel G. B. , Tuckett David
Published: March 2021

How do people form expectations about the future? We use amateur and expert investors' expectations about financial asset prices to study this question. Three experiments contrast therational expectationsassumption from neoclassical economics (investors forecast according to neoclassical financial theory) against two psychological theories of expectation formation—behaviorally informed expectations(investors understand empirical market anomalies and expect these anomalies to occur) andnarrative expectations(investors use narrative thinking to predict future prices). Whereas neoclassical financial theory maintains that past public information cannot be used to predict future prices, participants used company performance information revealedbeforea base price quotation to project future price trends after that quotation (Experiment 1), contradicting rational expectations. Importantly, these projections were stronger when information concerned predictions about a company's future performance rather than actual data about its past performance, suggesting that people not only rely on financially irrelevant (but narratively relevant) information for making predictions but erroneously impose temporal order on that information. These biased predictions had downstream consequences for asset allocation choices (Experiment 2), and these choices were driven in part by affective reactions to the company performance news (Experiment 3). There were some mild effects of expertise, but overall the effects of narrative appear to be consistent across all levels of expertise studied, including professional financial analysts. We conclude by discussing the prospects for a narrative theory of choice that provide new microfoundational insights about economic behavior.
The left digit effect in a complex judgment task: Evaluating hypothetical college applicants
Authors: Patalano Andrea L. , Williams Katherine , Weeks Gillian , Kayton Kelsey , Barth Hilary
Published: March 2021

A left digit effect has been broadly observed across judgment and decision‐making contexts ranging from product evaluation to medical treatment decisions to number line estimation. For example, $3.00 is judged to be a much greater cost than $2.99, and “801” is estimated strikingly too far to the right of “798” on a number line. Although the consequences of the effects for judgment and decision behavior have been documented, the sources of the effects are not well established. The goal of the current work is to extend investigations of the left digit effect to a new complex judgment activity and to assess whether the magnitude of the effect at the individual level can be predicted from performance on a simpler number skills task on which the left digit effect has also recently been observed. In three experiments (N = 434), adults completed a judgment task in which they rated the strength of hypothetical applicants for college admission and a self‐paced number line estimation task. In all experiments, a small or medium left digit effect was found in the college admissions task, and a large effect was found in number line estimation. Individual‐level variation was observed, but there was no relationship between the magnitudes of the effects in the two tasks. These findings provide evidence of a left digit effect in a novel multiattribute judgment task but offer no evidence that such performance can be predicted from a simple number skills task such as number line estimation.
Entorhinal cortex and parahippocampus volume reductions impact olfactory decline in aged subjects
Authors: Iizuka Natsuko , Masaoka Yuri , Kubota Satomi , Sugiyama Haruko , Yoshida Masaki , Yoshikawa Akira , Koiwa Nobuyoshi , Honma Motoyasu , Watanabe Keiko , Kamijo Shotaro , Kamimura Sawa , Ida Masahiro , Ono Kenjiro , Izumizaki Masahiko
Published: March 2021

Introduction

Pathological abnormalities first appear in the medial temporal regions including entorhinal cortex and parahippocampus in patients with Alzheimer's disease. Previous studies showed that olfactory decline in elderly subjects was associated with volume reductions in the left hippocampus and left parahippocampus without cognitive impairment. The aim of this study is to investigate the link between olfaction and volume reductions in the medial temporal regions including the parahippocampus, entorhinal cortex, and hippocampal subfields.

Method

27 elderly subjects and 27 young controls were measured olfaction acuity, cognitive function, and structural magnetic resonance imaging. Image processing and gray matter volumetric segmentation were performed with FreeSurfer. Volume data were analyzed with SPSS Statistics software.

Results

Interesting results of this study were that volume reduction in the entorhinal cortex was not directly linked with declining olfactory ability. Volume reduction in the left entorhinal cortex was correlated with volume reduction in the left parahippocampus and dentate gyrus. However, left parahippocampus volume reduction had the greatest impact on olfactory decline, and the entorhinal cortex and dentate gyrus might additionally contribute to olfactory decline.

Conclusion

Our results indicate that olfactory decline may be directly reflected in the medial temporal regions as reduced parahippocampus volumes, rather than as morphological changes in the entorhinal cortex and hippocampus. The parahippocampus may play an important role in the association between memory retrieval and olfactory identification.
Diversity and equity in Ibero‐American universities: An ecological analysis and proposals for action‐research from psychology
Authors: Garrido Rocío , Prado Marco Aurélio Máximo , Chaparro Reynel Alexander
Published: March 2021

Despite the numerous advances towards the recognition of LGBT rights worldwide, real equity has not yet been achieved. It is therefore necessary to take into consideration not only the socio‐political context but also the concrete practices that have been developed in specific settings. The university represents an important scene, which generates knowledge and development in societies. This study, from a Liberating Community Psychology approach, analysed five good practices related to LGBT issues and psychology placed in four countries with different socio‐cultural backgrounds: Brazil, Uruguay, Colombia and Spain. The results from an ecological SWOT analysis—based on interviews and questionnaires with diverse stakeholders and experts—showed the internal weaknesses (e.g., lack of resources) and strengths (e.g., high promoters' commitment, students acceptance) of the good practices, as well as their external opportunities and threats in the academic (e.g., social status of the university, curricula gaps), but also in the socio‐political context (e.g., protecting policies, attacks from conservative sectors). Additionally, action‐research proposals to improve equity in/from universities were suggested by stakeholders and prioritized by experts through a Delphi panel. The main theoretical and practical contributions are discussed. Please refer to the Supplementary Material section to find this article's Community and Social Impact Statement.
Synthesis of Uniform Gold Nanorods with Large Width to Realize Ultralow SERS Detection
Authors: He Hongpeng , Wu Chenshuo , Bi Cuixia , Song Yahui , Wang Dayang , Xia Haibing
Published: March 2021

In this work, we successfully demonstrate high‐yield synthesis of high‐quality gold nanorods (Au NRs) with width ranging from 6.5 nm to 175 nm by introducing heptanol molecules as secondary templating agents during cetyltrimethylammonium bromide‐templated, seeded growth method. The results show that an appropriate concentration of heptanol molecules not only alter the micellization behavior of CTAB in water, but also help silver ions impact the symmetry‐breaking efficiency of additional Au−NP seeds in addition to enhancing the utilization of gold precursors. Moreover, the generality and versatility of the present strategy for synthesis of Au NRs with flexible controlled dimensions are further demonstrated by successful synthesis of Au NRs with the assistance of other fatty alcohols with properly long alkyl chains. Furthermore, when arrays of vertically aligned Au NRs with large width (AVA−Au120×90 NRs) are used as SERS substrates, they can achieve the ultralow limit of detection for crystal violet (10−16 M) with good reliability and reproducibility, and the rapid detection and identification of residual harmful substances.
Orbital‐Free Quantum Crystallographic View on Noncovalent Bonding: Insights into Hydrogen Bonds, π⋅⋅⋅π and Reverse Electron Lone Pair⋅⋅⋅π Interactions
Authors: Shteingolts Sergey A. , Stash Adam I. , Tsirelson Vladimir G. , Fayzullin Robert R.
Published: March 2021

A detailed analysis of a complete set of the local potentials that appear in the Euler equation for electron density is carried out for noncovalent interactions in the crystal of a uracil derivative using experimental X‐ray charge density. The interplay between the quantum theory of atoms in molecules and crystals and the local potentials and corresponding inner‐crystal electronic forces of electrostatic and kinetic origin is explored. Partitioning of crystal space into atomic basins and atomic‐like potential basins led us to the definite description of interatomic interaction and charge transfer. Novel physically grounded bonding descriptors derived within the orbital‐free quantum crystallography provided the detailed examination of π‐stacking and intricate C=O⋅⋅⋅π interactions and nonclassical hydrogen bonds present in the crystal. The donor‐acceptor character of these interactions is revealed by analysis of Pauli and von Weizsäcker potentials together with well‐known functions, e. g., deformation electron density and electron localization function. In this way, our analysis throws light on aspects of these closed‐shell interactions hitherto hidden from the description.
Molecular Tools for the Study of ADP‐Ribosylation: A Unified and Versatile Method to Synthesise Native Mono‐ADP‐Ribosylated Peptides
Authors: Voorneveld Jim , Rack Johannes Gregor Matthias , van Gijlswijk Luke , Meeuwenoord Nico J. , Liu Qiang , Overkleeft Herman S. , van der Marel Gijsbert A. , Ahel Ivan , Filippov Dmitri V.
Published: March 2021

ADP‐ribosylation (ADPr), as a post‐translational modification, plays a crucial role in DNA‐repair, immunity and many other cellular and physiological processes. Serine is the main acceptor for ADPr in DNA damage response, whereas the physiological impact of less common ADPr‐modifications of cysteine and threonine side chains is less clear. Generally, gaining molecular insights into ADPr recognition and turn‐over is hampered by the availability of homogeneous, ADP‐ribosylated material, such as mono‐ADP‐ribosylated (MARylated) peptides. Here, a new and efficient solid‐phase strategy for the synthesis of Ser‐, Thr‐ and Cys‐MARylated peptides is described. ADP‐ribosylated cysteine, apart from being a native post‐translational modification in its own right, proved to be suitable as a stabile bioisostere for ADP‐ribosylated serine making it a useful tool to further biochemical research on serine ADP‐ribosylation. In addition, it was discovered that the Streptococcus pyogenes encoded protein, SpyMacroD, acts as a Cys‐(ADP‐ribosyl) hydrolase.
Azide‐Functionalized Derivatives of the Virulence‐Associated Sugar Pseudaminic Acid: Chiral Pool Synthesis and Labeling of Bacteria
Authors: Vibhute Amol M. , Tamai Hideki , Logviniuk Dana , Jones Peter G. , Fridman Micha , Werz Daniel B.
Published: March 2021

Pseudaminic acid (Pse) is a significant prokaryotic monosaccharide found in important Gram‐negative and Gram‐positive bacteria. This unique sugar serves as a component of cell‐surface‐associated glycans or glycoproteins and is associated with their virulence. We report the synthesis of azidoacetamido‐functionalized Pse derivatives as part of a search for Pse‐derived metabolic labeling reagents. The synthesis was initiated with d‐glucose (Glc), which served as a cost‐effective chiral pool starting material. Key synthetic steps involve the conversion of C1 of Glc into the terminal methyl group of Pse, and inverting deoxyaminations at C3 and C5 of Glc followed by backbone elongation with a three‐carbon unit using the Barbier reaction. Metabolic labeling experiments revealed that, of the four Pse derivatives, ester‐protected C5 azidoacetamido‐Pse successfully labeled cells of Pse‐expressing Gram‐positive and Gram‐negative strains. No labeling was observed in cells of non‐Pse‐expressing strains. The ester‐protected and C5 azidoacetamido‐functionalized Pse is thus a useful reagent for the identification of bacteria expressing this unique virulence‐associated nonulosonic acid.
Interconnectivity between Surface Reactivity and Self‐Assembly of Kemp Elimination Catalyzing Nanorods
Authors: Shandilya Ekta , Dasgupta Basundhara , Maiti Subhabrata
Published: March 2021

Understanding the fundamental facts behind dynamicity of catalytic processes has been a longstanding quest across disciplines. Herein, we report self‐assembly of catalytically active gold nanorods that can be regulated by tuning its reactivity towards a proton transfer reaction at different pH. Unlike substrate‐induced templating and co‐operativity, the enhanced aggregation rate is due to alteration of catalytic surface charge only during reactivity as negatively charged transition state of reactant (5‐nitrobenzisoxazole) is formed on positively charged nanorod while undergoing a concerted E2‐pathway. Herein, enhanced diffusivity during catalytic processes might also act as an additional contributing factor. Furthermore, we have also shown that nanosized hydrophobic cavities of clustered nanorods can also efficiently accelerate the rate of an aromatic nucleophilic substitution reaction, which also demonstrates a catalytic phenomenon that can lead to cascading of other reactions where substrates and products of the starting reactions are not directly involved.
Reaction Mechanisms of the Degradation of Fluoroethylene Carbonate, an Additive of Lithium‐Ion Batteries, Unraveled by Radiation Chemistry
Authors: Puget Marin , Shcherbakov Viacheslav , Denisov Sergey , Moreau Philippe , Dognon Jean‐Pierre , Mostafavi Mehran , Le Caër Sophie
Published: March 2021

Numerous additives are used in the electrolytes of lithium‐ion batteries, especially for the formation of an efficient solid electrolyte interphase at the surface of the electrodes. Understanding the degradation processes of these compounds is thus important; they can be seen through radiolysis. In the case of fluoroethylene carbonate (FEC), picosecond pulse radiolysis experiments evidenced the formation of FEC.−. This radical is stabilized in neat FEC, whereas the ring opens to form more stable radical anions when FEC is a solute in other solvents, as confirmed by quantum chemistry calculations. In neat FEC, pre‐solvated electrons primarily undergo attachment rather than solvation. On long timescales, the gases produced (H2, CO, and CO2) were quantified. A reaction scheme for both the oxidizing and reducing pathways at stake in irradiated FEC is proposed. This work shows that the nature of the primary species formed in FEC depends on the amount of FEC in the solution.
Rhamnogalacturonan II: Chemical Synthesis of a Substructure Including α‐2,3‐Linked Kdo**
Authors: Mancuso Enzo , Romanò Cecilia , Trattnig Nino , Gritsch Philipp , Kosma Paul , Clausen Mads H.
Published: March 2021

The synthesis of a fully deprotected Kdo‐containing rhamnogalacturonan II pentasaccharide is described. The strategy relies on the preparation of a suitably protected homogalacturonan tetrasaccharide backbone, through a post‐glycosylation oxidation approach, and its stereoselective glycosylation with a Kdo fluoride donor.
Reevaluating the Solution Photophysics of Tetraphenylethylene at the Origin of their Aggregation‐Induced Emission Properties
Authors: Rouillon Jean , Monnereau Cyrille , Andraud Chantal
Published: March 2021

Although tetraphenylethylene (TPE) and its derivatives have been the most commonly used building blocks in the construction of molecules with aggregation‐induced emission (AIE) properties, no absolute consensus exists regarding the mechanisms at the origin of the phenomenon. Restriction of intramolecular rotations (RIR) of peripheral phenyls has historically been a dominant paradigm, which has served as a valuable guideline in the molecular engineering of AIEgens. Yet, an increasing number of recent works have established that photoisomerization or photocyclization may actively participate in the nonradiative dissipation of the excitation energy. In this paper, the first experimental evaluation of the quantum efficiencies of these different processes is reported, and photoisomerization is shown to be by far the dominant photophysical pathway in solution, accounting for virtually all nonradiative decay of the molecule‘s excited state in degassed solution.
Synthesis and Structure of an o‐Carboranyl‐Substituted Three‐Coordinate Borane Radical Anion
Authors: Krebs Johannes , Haehnel Martin , Krummenacher Ivo , Friedrich Alexandra , Braunschweig Holger , Finze Maik , Ji Lei , Marder Todd B.
Published: March 2021

Bis(1‐(4‐tolyl)‐carboran‐2‐yl)‐(4‐tolyl)‐borane [(1‐(4‐MeC6H4)‐closo‐1,2‐C2B10H10‐2‐)2(4‐MeC6H4)B] (1), a new bis(o‐carboranyl)‐(R)‐borane was synthesised by lithiation of the o‐carboranyl precursor and subsequent salt metathesis reaction with (4‐tolyl)BBr2. Cyclic voltammetry experiments on 1 show multiple distinct reduction events with a one‐electron first reduction. In a selective reduction experiment the corresponding paramagnetic radical anion 1.− was isolated and characterized. Single‐crystal structure analyses allow an in‐depth comparison of 1, 1.−, their calculated geometries, and the S1 excited state of 1. Photophysical studies of 1 show a charge transfer (CT) emission with low quantum yield in solution but a strong increase in the solid state. TD‐DFT calculations were used to identify transition‐relevant orbitals.
Rerouting and Improving Dauc‐8‐en‐11‐ol Synthase from Streptomyces venezuelae to a High Yielding Biocatalyst
Authors: Lauterbach Lukas , Hou Anwei , Dickschat Jeroen S.
Published: March 2021

The dauc‐8‐en‐11‐ol synthase from Streptomyces venezuelae was investigated for its catalytic activity towards alternative terpene precursors, specifically designed to enable new cyclisation pathways. Exchange of aromatic amino acid residues at the enzyme surface by site‐directed mutagenesis led to a 4‐fold increase of the yield in preparative scale incubations, which likely results from an increased enzyme stability instead of improved enzyme kinetics.
Topology Effects in Molecular Organic Electronic Materials: Pyrene and Azupyrene**
Authors: Klein Benedikt P. , Ruppenthal Lukas , Hall Samuel J. , Sattler Lars E. , Weber Sebastian M. , Herritsch Jan , Jaegermann Andrea , Maurer Reinhard J. , Hilt Gerhard , Gottfried J. Michael
Published: March 2021

Pyrene derivatives play a prominent role in organic electronic devices, including field effect transistors, light emitting diodes, and solar cells. The flexibility in the desired properties has previously been achieved by variation of substituents at the periphery of the pyrene backbone. In contrast, the influence of the topology of the central π‐electron system on the relevant properties such as the band gap or the fluorescence behavior has not yet been addressed. In this work, pyrene is compared with its structural isomer azupyrene, which has a π‐electron system with non‐alternant topology. Using photoelectron spectroscopy, near edge X‐ray absorption fine structure spectroscopy, and other methods, it is shown that the electronic band gap of azupyrene is by 0.72 eV smaller than that of pyrene. The difference of the optical band gaps is even larger with 1.09 eV, as determined by ultraviolet–visible absorption spectroscopy. The non‐alternant nature of azupyrene is also associated with a more localized charge distribution. Further insight is provided by density functional theory (DFT) calculations of the molecular properties and ab initio coupled cluster calculations of the optical transitions. The concept of aromaticity is used to interpret the major topology‐related differences.
Isolation of HLA Bound Peptides by Immunoaffinity Capture and Identification by Mass Spectrometry
Authors: Pandey Kirti , Ramarathinam Sri H. , Purcell Anthony W.
Published: March 2021

This article describes the purification of HLA‐bound peptides and their subsequent sequencing by mass spectrometry. These methods can be used for both HLA class I and class II molecules and can be adapted to different species depending on the availability of specific antibodies. Peptides can be successfully isolated from a variety of sample types, including in vitro cultured cells and primary tissues. The method involves the affinity capture of HLA‐peptide complexes and separation of peptides from HLA heavy chains, followed by tailored interrogation by mass spectrometry to take into account the non‐tryptic nature of endogenously derived HLA‐bound peptides. © 2021 Wiley Periodicals LLC.

Basic Protocol 1: Preparation of immunoaffinity column

Alternate Protocol 1: Preparation of microscale immunoaffinity column

Basic Protocol 2: Generation of cell lysate and HLA immunoaffinity purification

Alternate Protocol 2: Microscale immunoaffinity purification

Basic Protocol 3: Separation of HLA peptides by reverse‐phase high‐performance liquid chromatography (RP‐HPLC)

Alternate Protocol 3: Isolation of HLA peptides using molecular weight cutoff (MWCO) filter

Basic Protocol 4: Mass spectrometry and data analysis
Characterization of mutations conferring inherent resistance to acetyl coenzyme A carboxylase‐inhibiting herbicides in turfgrass and grassy weeds
Authors: Tate Trent M. , McCullough Patrick E. , Harrison Melanie L. , Chen Zhenbang , Raymer Paul L.
Published: March 2021

An herbicide‐resistant weed control system that utilizes naturally occurring mutations to acetyl‐coenzyme A carboxylase (ACCase)‐inhibiting herbicides could provide herbicide selectivity and improve control of grassy weeds in turf. Knowledge regarding the presence of these mutations in grasses is needed to guide development of this type of system. This research subjected 24 species of warm‐season, cool‐season, and grassy weed species to rates of 0, 400, and 1200 g a.i. ha−1 of fenoxaprop herbicide and surveyed these species for the presence of site‐of‐action mutations in ACCase at amino acid (aa) positions 1781, 1999, 2027, 2041, 2076, 2088, and 2096. Nine species including Agrostis capillaris L., Festuca ovina L., Festuca rubra L., Lolium multiflorum Lam., Lolium perenne L., Paspalum dilatatum Poir., Poa annua L., Zoysia japonica Steud., and Z. matrella [L.] Merr. were tolerant to fenoxaprop. Site of action point mutations conferring resistance to ACCase herbicides were found at aa position 1781 in only three of 24 species surveyed (Festuca ovina, Festuca rubra, and Poa annua). The information obtained from this study provide guidance for the development of ACCase resistant weed control systems for turfgrass.
Niche separation and weak interactions in the high tidal zone of saltmarsh‐mangrove mixing communities
Authors: Ndayambaje Patrick , Wei Lili , Zhang Tingfeng , Li Yuhong , Liu Lin , Huang Xu , Liu Chaoxiang
Published: March 2021

Saltmarsh‐mangrove ecotones occur at the boundary of the natural geographic distribution of mangroves and salt marshes. Climate warming and species invasion can also drive the formation of saltmarsh‐mangrove mixing communities. How these coastal species live together in a “new” mixed community is important in predicting the dynamic of saltmarsh‐mangrove ecosystems as affected by ongoing climate change or human activities. To date, the understanding of species interactions has been rare on adult species in these ecotones.

Two typical coastal wetlands were selected as cases to understand how mangrove and saltmarsh species living together in the ecotones. The leaves of seven species were sampled from these coastal wetlands based on their distribution patterns (living alone or coexisting) in the high tidal zone, and seven commonly used functional traits of these species were analyzed.

We found niche separation between saltmarsh and mangrove species, which is probably due to the different adaptive strategies they adopted to deal with intertidal environments.

Weak interactions between coexisting species were dominated in the high tidal zone of the two saltmarsh‐mangrove communities, which could be driven by both niche differentiation and neutral theory.

Synthesis. Our field study implies a potential opportunity to establish a multispecies community in the high tidal zone of saltmarsh‐mangrove ecotones, where the sediment was characterized by low salinity and high nitrogen.
Change in ejection fraction and long‐term mortality in adults referred for echocardiography
Authors: Strange Geoff , Playford David , Scalia Gregory M. , Celermajer David S. , Prior David , Codde Jim , Chan Yih‐Kai , Bulsara Max K. , Stewart Simon ,   the NEDA Investigators
Published: March 2021

Aims

We investigated long‐term mortality associated with changes in left ventricular ejection fraction (LVEF) in a large, real‐world patient cohort.

Methods and results

A total of 117 275 adults (63 ± 16 years, 46% women) had LVEF quantified by the same method ≥6 months apart. This included 17 343 cases (66 ± 15 years, 48% women) being initially investigated for heart failure (HF). During 3.3 [interquartile range (IQR) 1.7–6.0] years from first to last echocardiogram, median change in LVEF was −1 (IQR −8 to +5) units from a baseline of 62% (IQR 54–69%). During subsequent 7.6 (IQR 4.3–10.1) years of follow‐up, 11 397 (9.7%) and 34 101 (29.1%) cases died from cardiovascular disease and all causes, respectively. Actual 5‐year, all‐cause mortality increased from 12% to 29% among those with the smallest to the largest decrease in LVEF (from <5 units to >30 units); the adjusted risk of cardiovascular‐related mortality increased two‐ to eightfold beyond a >10‐unit decline in LVEF (vs. minimal change; P < 0.001 for all comparisons). Among those initially investigated for HF (32% with initial LVEF <50%), the adjusted hazard ratio for cardiovascular‐related mortality ranged from 0.35 [95% confidence interval (CI) 0.28–0.49] to 4.21 (95% CI 3.30–5.22) for a >30‐unit increase to >30‐unit decline in LVEF (vs. minimal change; P < 0.001 for both comparisons). A distinctive, bi‐directional plateau of improved vs. worsening mortality was evident around a final LVEF of 50% to 55%.

Conclusions

These data, derived from a large, heterogeneous cohort of adults being followed up with echocardiography, suggest that modest LVEF changes (particularly around an LVEF of 50–55%) may be of clinical significance.
Virtual optimization of guideline‐directed medical therapy in hospitalized patients with heart failure with reduced ejection fraction: the IMPLEMENT‐HF pilot study
Authors: Bhatt Ankeet S. , Varshney Anubodh S. , Nekoui Mahan , Moscone Alea , Cunningham Jonathan W. , Jering Karola S. , Patel Parth N. , Sinnenberg Lauren E. , Bernier Thomas D. , Buckley Leo F. , Cook Bryan M. , Dempsey Jillian , Kelly Julie , Knowles Danielle M. , Lupi Kenneth , Malloy Rhynn , Matta Lina S. , Rhoten Megan N. , Sharma Krishan , Snyder Caroline A. , Ting Clara , McElrath Erin E. , Amato Mary G. , Alobaidly Maryam , Ulbricht Catherine E. , Choudhry Niteesh K. , Adler Dale S. , Vaduganathan Muthiah
Published: March 2021

Aims

Implementation of guideline‐directed medical therapy (GDMT) for heart failure with reduced ejection fraction (HFrEF) remains incomplete. Non‐cardiovascular hospitalization may present opportunities for GDMT optimization. We assessed the efficacy and durability of a virtual, multidisciplinary ‘GDMT Team’ on medical therapy prescription for HFrEF.

Methods and results

Consecutive hospitalizations in patients with HFrEF (ejection fraction ≤40%) were prospectively identified from 3 February to 1 March 2020 (usual care group) and 2 March to 28 August 2020 (intervention group). Patients with critical illness, de novo heart failure, and systolic blood pressure <90 mmHg in the preceeding 24 hs prior to enrollment were excluded. In the intervention group, a pharmacist–physician GDMT Team provided optimization suggestions to treating teams based on an evidence‐based algorithm. The primary outcome was a GDMT optimization score, the sum of positive (+1 for new initiations or up‐titrations) and negative therapeutic changes (−1 for discontinuations or down‐titrations) at hospital discharge. Serious in‐hospital safety events were assessed. Among 278 consecutive encounters with HFrEF, 118 met eligibility criteria; 29 (25%) received usual care and 89 (75%) received the GDMT Team intervention. Among usual care encounters, there were no changes in GDMT prescription during hospitalization. In the intervention group, β‐blocker (72% to 88%; P = 0.01), angiotensin receptor–neprilysin inhibitor (6% to 17%; P = 0.03), mineralocorticoid receptor antagonist (16% to 29%; P = 0.05), and triple therapy (9% to 26%; P < 0.01) prescriptions increased during hospitalization. After adjustment for clinically relevant covariates, the GDMT Team was associated with an increase in GDMT optimization score (+0.58; 95% confidence interval +0.09 to +1.07; P = 0.02). There were no serious in‐hospital adverse events.

Conclusions

Non‐cardiovascular hospitalizations are a potentially safe and effective setting for GDMT optimization. A virtual GDMT Team was associated with improved heart failure therapeutic optimization. This implementation strategy warrants testing in a prospective randomized controlled trial.
One‐Pot Oxidation of Secondary Alcohols to α‐Hydroxy Ketones: Application to Synthesis of Oxoaplysinopsin D, E, F, & G
Authors: Kulkarni Akshay S. , Ramesh Eagala , Srinivasa Reddy D.
Published: March 2021

A simple one‐pot transformation of secondary alcohols to α‐hydroxy ketones using pyridinium dichromate (PDC) in DMF has been developed and substrate scope tested with 25 compounds of hydantoin derivatives. Using this method, we have devised a common dihydroxy intermediate and synthesized four natural products oxoaplysinopsins D, E, F, and G for the first time.
Stopped‐Flow 19F NMR Spectroscopic Analysis of a Protodeboronation Proceeding at the Sub‐Second Time‐Scale
Authors: Wei Ran , Hall Andrew M. R. , Behrens Richard , Pritchard Mark S. , King Edward J. , Lloyd‐Jones Guy C.
Published: March 2021

In‐situ NMR spectroscopic analysis of homogeneous reactions is an essential tool for mechanistic analysis in organic and organometallic chemistry. However, rapid non‐equilibrium reactions, that are initiated by mixing, require specialized approaches. We report herein on a study of the factors that ensure quantitative results in a recently‐developed technique for stopped‐flow NMR spectroscopy. The influence of some of the key parameters on quantitation is studied by 19F NMR spectroscopic analysis of the kinetics and activation parameters for the base‐catalyzed protodeboronation of highly‐reactive polyfluorinated arylboronic acids, with half‐lives as low as 0.1 seconds. The effects of spin relaxation, pre‐magnetization, heat‐transfer versus reaction enthalpy, and mixing‐efficiency are analyzed in detail. We also compare and contrast choice of pulse angle, interscan delay, and use of pseudo real‐time by interleaving, as means to achieve an optimal balance between temporal resolution and sensitivity.
A Synthetic Route to Benzothiazocines with Two or Three Carbon Stereocenters via Copper‐Catalyzed Intramolecular N‐Arylation
Authors: Choury Mickael , Blond Gaëlle , Gulea Mihaela
Published: March 2021

A new structural family of benzothiazocines bearing two or three carbon stereogenic centers on the 8‐membered ring was synthesized by intramolecular Cu‐catalyzed N‐arylation. The chiral racemic 1,3‐aminothioethers precursors have been prepared from easily available starting materials. An ionic organic base was used for the first time in an intramolecular C−N coupling, in medium‐ring series, leading to higher yields than those obtained with an inorganic base, and a partial epimerization in some cases. The synthetic sequence was successfully performed on one example in asymmetric version, demonstrating the accessibility of enantioenriched benzothiazocines.
Application of a Thiadiazole‐derivative in a Tyrosinase‐based Amperometric Biosensor for Epinephrine Detection
Authors: Meloni Francesca , Spychalska Kamila , Zając Dorota , Pilo Maria Itria , Zucca Antonio , Cabaj Joanna
Published: March 2021

Enzyme‐based amperometric biosensors are proving to be important analytical tools in several fields such as food, environmental and, in recent years, the biomedical one. This work describes the use of 4,7‐bis(5‐(pyridin‐2‐yl)thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole (TBT) in the development of a tyrosinase‐based biosensor for epinephrine detection. The modifying agent was obtained as a film by electrochemical oxidation of TBT on a gold disk electrode. Electrochemical characterization and scanning electrode microscopy (SEM) images suggest the formation of a conducting film on the electrode surface. Tyrosinase from mushroom was then immobilized by a mixed technique of adsorption and cross‐linking. Glutaraldehyde was used as a coupling agent. The obtained device shows a very good linear response (0.1–50 μM) with a LoD value of 0.06 μM and a LoQ of 0.09 μM. Moreover, good selectivity towards some typical interferents (namely, ascorbic acid, tryptophan, uric acid and L‐cysteine) and satisfactory recoveries have been observed.
Vertebrate herbivory weakens directional selection for earlier emergence in competition
Authors: Waterton Joseph , Cleland Elsa E.
Published: March 2021

The timing of seedling emergence is strongly linked with fitness because it determines the biotic and abiotic environment experienced by plants in this vulnerable life stage. Experiments and observations consistently find that earlier-emerging plants have a competitive advantage over those emerging later. However, substantial genetic and phenotypic variation in emergence timing is harbored within and among plant populations, making it important to characterize the selective agents—including biotic interactions—that contribute to this variation. In seasonal herbaceous communities, we hypothesized that consumption of early-emerging individuals by vertebrates could weaken the strength of directional selection for earlier emergence in competitive environments. To investigate this, we carried out phenotypic selection analyses on emergence timing in two California grass species, the native Stipa pulchra and non-native Bromus diandrus, growing in intraspecific competitive neighborhoods with and without vertebrate herbivore exclusion. Vertebrate herbivores consistently weakened directional selection for earlier emergence. Our results demonstrate that vertebrate herbivores play an underappreciated selective role on phenology in plant populations, with implications for contemporary evolution, such as the potential of species to adapt to global environmental changes.
Natural convection and entropy generation in square and skew cavities due to large temperature differences: A Gay–Lussac‐type vorticity stream‐function approach
Authors: Mayeli Peyman , Sheard Gregory J.
Published: March 2021

In this study, a benchmark natural convection problem is studied under a Gay–Lussac‐type approximation incorporating centrifugal effects in the context of a new vorticity‐stream‐function approach. This approximation differs from the classic Boussinesq approximation in that density variations are considered in the advection term as well as the gravity term in the momentum equations. Such a treatment invokes Froude number as a non‐Boussinesq parameter deviating results from the classic Boussinesq approximation. It is also shown how the Gay–Lussac parameter may be expressed by its equivalent relative temperature difference. Numerical simulation of natural convection in square and skewed cavities are performed up to Ra = 106 and ϵ = 0.3 at Pr = 0.71. Results obtained with new approximation are compared against the weakly compressible approach and the conventional Boussinesq approximation in terms of the average and local Nusselt number, coefficient of friction and entropy generation. Comparing the local Nusselt number indicates a negligible difference between Gay–Lussac type and the Boussinesq approximations even at a high relative temperature difference, with both deviating from the weakly compressible approach. Comparing coefficient friction results obtained by the Gay–Lussac‐type approximation against the weakly compressible approach confirms superior numerical data in some regions of the physical domain with less deviation for rotating flows in comparison with the Boussinesq approximation. Finally, comparing the computational cost of the numerical simulation shows at least 8% less computational cost when governing equations are solved via secondary variables using a central scheme rather than primitive variables.
Time‐varying dynamics of expected shortfall in commodity futures markets
Authors: Mehlitz Julia S. , Auer Benjamin R.
Published: March 2021

Motivated by the growing interest of investors in commodities and by advances in risk measurement, we present a full‐scale analysis of expected shortfall (ES) in commodity futures markets. Besides illustrating the dynamics of historic ES, we evaluate whether popular estimators are suitable for forecasting future ES. By implementing a new backtest, we find that the performance of estimators hinges on market stability. Estimators tend to fail when markets are in turmoil and accurate forecasts are urgently needed. Even though a kernel method performs best on average, our results advise against the use of established estimators for risk (and margin) prediction.
Bestimmung von Gebirgsspannungen mit dem Überbohrverfahren – Teil 1: Triaxialmesssonden – Neufassung der Empfehlung Nr. 14 des Arbeitskreises „Versuchstechnik Fels“ der DGGT
Authors: Kiehl Johannes R. , Heusermann Stefan
Published: March 2021

Der Arbeitskreis AK 3.3 „Versuchstechnik Fels“ der Deutschen Gesellschaft für Geotechnik e. V. erarbeitet Empfehlungen für felsmechanische Labor‐ und Feldversuche sowie Messungen im Gebirge und an geotechnischen Bauwerken. Die vorliegende Neufassung der Empfehlung Nr. 14 behandelt Überbohrversuche zur Bestimmung von Gebirgsspannungen und berücksichtigt die Weiterentwicklung der Versuchstechnik seit der Herausgabe der Empfehlung Nr. 14 „Überbohr‐Entlastungsversuche zur Bestimmung von Gebirgsspannungen“ im Jahre 1990 [1]. Es werden die Anforderungen an die Messgeräte sowie die Vorgehensweise für die Durchführung und Auswertung dieser Versuche festgelegt. Es wird auf die Empfehlungen der International Society for Rock Mechanics (ISRM), in denen Überbohrversuche behandelt werden, hingewiesen [2, 3]. Die Empfehlung Nr. 14 ist in zwei Teile gegliedert. Im vorliegenden Teil 1 werden Überbohrversuche mithilfe von Triaxialmesssonden behandelt. Der Teil 2 dieser Empfehlung befasst sich mit Überbohrversuchen mittels Weggebersonden.
Maturity and thermal evolution differences between two sets of Lower Palaeozoic shales and its significance for shale gas formation in south‐western Sichuan Basin, China
Authors: Wang Ye , Qiu Nansheng , Xie Xiaomin , Ma Zhongliang , Li Longlong , Feng Qianqian , Yang Liu , Shen Baojian , Borjigin Tenger , Tao Ni
Published: March 2021

Abtract

The Lower Cambrian Qiongzhusi shale and the Upper Ordovician–Lower Silurian Wufeng‐Longmaxi shale are major source rocks and important shale gas exploration targets in the Sichuan Basin. Cutting and core samples from two shale gas wells in south‐western Sichuan Basin have been selected for organic matter (OM) reflectance measurement and Raman spectra analysis with the aim to determine maturity. The results were incorporated for basin modelling to construct the thermal evolution of this area. Graptolite fragments and pyrobitumens are the dominant form of OM in Wufeng‐Longmaxi shale. A limited number of the OM as pyrobitumens and vitrinite‐like particles is presented in Qiongzhusi shale. According to the measured reflectance of OM in conjunction with the maturity calculated using Raman spectra, the equivalent vitrinite reflectance (EqVRo) values based on solid bitumen and graptolite is 2.53–2.81% for the Wufeng‐Longmaxi shale. The EqVRo value is 2.85–3.53% within 300 m depth intervals for the Qiongzhusi shale. A significant difference in oil generation occurred before the Late Permian between Qiongzhusi shale and Wufeng‐Longmaxi shale based on basin modelling and reassessment of previous published data. Compared with the Qiongzhusi shale, the Wufeng‐Longmaxi shale would have lower maturities before Late Permian and less hydrocarbon could be generated/expelled at that time, therefore, this shale remained with a large amount of oil, which could crack into gas. This difference had shown a favourable time relationship for generation and accumulation of shale gas in Wufeng‐Longmaxi shale.
Insulin resistance accounts for metabolic syndrome‐related alterations in brain structure
Authors: Lu Ran , Aziz N. Ahmad , Diers Kersten , Stöcker Tony , Reuter Martin , Breteler Monique M.B.
Published: March 2021

Metabolic syndrome (MetS) is a major public health burden worldwide and associated with brain abnormalities. Although insulin resistance is considered a pivotal feature of MetS, its role in the pathogenesis of MetS‐related brain alterations in the general population is unclear. Therefore, in 973 participants (mean age 52.5 years) of the population‐based Rhineland Study, we assessed brain morphology in relation to MetS and insulin resistance, and evaluated to what extent the pattern of structural brain changes seen in MetS overlap with those associated with insulin resistance. Cortical reconstruction and volumetric segmentation were obtained from high‐resolution brain images at 3 Tesla using FreeSurfer. The relations between metabolic measures and brain structure were assessed through (generalized) linear models. Both MetS and insulin resistance were associated with smaller cortical gray matter volume and thickness, but not with white matter or subcortical gray matter volume. Age‐ and sex‐adjusted vertex‐based brain morphometry demonstrated that MetS and insulin resistance were related to cortical thinning in a similar spatial pattern. Importantly, no independent effect of MetS on cortical gray matter was observed beyond the effect of insulin resistance. Our findings suggest that addressing insulin resistance is critical in the prevention of MetS‐related brain changes in later life.
Comparison of dipstick and quantitative tests for proteinuria and hematuria in middle‐aged, male Japanese employees: A single‐center study
Authors: Ikeda Kanako , Abe Masaharu , Masamoto Izumi , Ishii Chikako , Arimura Emi , Ushikai Miharu , Oketani Kaoru , Hashiguchi Teruto , Horiuchi Masahisa
Published: March 2021

Background and Aims

The early and reliable detection of chronic kidney disease is important. In the present study, we aimed to compare the diagnostic results for proteinuria and hematuria between the dipstick test used in primary occupational health examinations and the quantitative tests used in more thorough examinations in clinics.

Methods

We conducted a single‐center observational study of male staff (N = 573) at Kagoshima University who underwent a health examination in 2017. Both dipsticks and biochemical methods were used to assess proteinuria and hematuria.

Results

For the dipstick test, the sensitivity, specificity, and positive predictive value were 55.6%, 92.4% and 10.4% for proteinuria, and 64.3%, 98.3% and 66.7% for hematuria, respectively. Four participants for whom false‐negative results were obtained using dipsticks for proteinuria, and two of these had 3+ urinary glucose.

Conclusion

Qualitative tests for proteinuria and hematuria had low sensitivities and positive predictive values. Therefore, for the early and reliable detection of chronic kidney disease, the use of quantitative urine tests should be considered during occupational health examinations.
Investigation on a small‐scale vertical tube evaporator multieffect desalination system: Modeling, analysis, and optimization
Authors: Deharkar Rahul , Mudgal Anurag , Patel Vivek K.
Published: March 2021

A growing population with depleting water resources has increased the requirement for desalination systems. Large‐scale desalination plants have seen a growth in the recent period; however, the small‐scale (SS) decentralized desalination plants' need has not been realized for the rural population. Low specific heat consumption for multieffect desalination systems makes it suitable for such decentralized operation. The challenge now lies in determining the system capacity and optimal operational range for the SS requirements. In this study, the thermoeconomic model for an SS multieffect desalination system for various configurations is developed. Optimization of the SS plant for the number of effects is performed to determine the optimal operational range of motive steam pressure, motive steam flow rate, and feed water flow rate. Total distillate production and freshwater cost are focused on objectives and constraints imposed over the input parameters with SS production. The results reveal that for a distillate production of 750 L/day, the motive steam flow requirement is estimated to be 25–35 kg/h with a pressure range of 2–5 bar. This study provided an overview for selecting the number of effects based on the commercial aspect of total production requirements.
EU bank insolvency law harmonisation: What next?
Authors: Schillig Michael
Published: March 2021

After the COVID‐19 crisis has subsided, the (further) harmonization of bank insolvency law will again be high on the agenda of EU regulators and policymakers. On the basis of an analysis of the status quo pain points, this article advocates the extension of the BRRD resolution regime to all bank failures, regardless of their systemic relevance. This could be achieved by removing the public interest requirement as part of the resolution trigger. The ensuing consolidation would significantly reduce complexity and enhance the transparency and legitimacy of the EU crisis management framework.