bluuebunny/crossref_metadata_2025 huggingface dataset:
Dual Self‐Healing Anticorrosion Coatings Based on Multibranched Waterborne Polyurethane and TiO2 Nanocapsule‐Loaded Graphene Oxide
Authors: Zhou Jianlin , Liu Han , Sun Yangyi , Chen Kunlin
Published: February 2022

The study reports the successful fabrication of a novel dual self‐healing anticorrosion coating based on benzotriazole loaded TiO2 nanocapsule (BTC) modified graphene oxide sheets and the multibranched waterborne polyurethane (WPU). When corrosion occurs, the benzotriazole (BZT) in nanocapsules can be slowly released from the coating forming a passivation layer on the metal surface to isolate the corrosive mediums. The anticorrosion performance of coating is examined by performing electrochemical tests. As indicated from the results, after being immersed in 3.5 wt% NaCl for 7 d, the prepared coating shows excellent anticorrosion performance with inhibition efficiency of 99%. In addition, the φ in 104 Hz increases from 10° to 30°, and Log|Z|0.01Hz remains at nearly 4.5 with the immersing time extended to 30 d. Moreover, when the coating is physically damaged, the damaged coating can be self‐repaired by the reversible disulfide bonds in WPU and the releasing of the BZT simultaneously. Compared with other control anticorrosion coatings, the healed coating achieves significantly improved anticorrosion performance, and the damaged coating can still sustain the original anticorrosion performance after self‐healing. This study proposes a novel fabrication strategy for self‐healing materials, and it can contribute to the long‐term use of anticorrosion coatings.
Optically Transparent Low Scattering Metasurface Based on Polarization Conversion‐Diffusion‐Absorption Integration Mechanism
Authors: Ran Yuzhou , Shi Lihua , Wu Shuran , Fan Bo , Jin Xin , Ji Dedong , Ma Yao , Li Jie , Liu Yicheng , Wang Jianbao
Published: February 2022

In this paper, an optically transparent low‐scattering metasurface combining polarization conversion, diffusion, and absorption mechanisms is proposed. Firstly, a polarization conversion absorbing meta‐atom is designed, and its reflection coefficient is optimized based on equivalent circuit theory and genetic algorithm. Then, by arranging the meta‐atom and its orthogonal structural meta‐atom according to the random coding sequence, the metasurface is constructed, realizing the design concept of co‐polarization absorption and cross‐polarization diffusion. The simulation results are in good agreement with the measured results and the Radar Cross Section (RCS) reduction of more than −10 and −25 dB can be realized in the co‐polarized and cross‐polarized directions in 3.3–12.3 GHz, respectively. Moreover, the amplitude and bandwidth of RCS reduction of the metasurface can be maintained well in the 0–40° oblique incidence range.
Cerebral oxygen metabolic stress is increased in children with sickle cell anemia compared to anemic controls
Authors: Fields Melanie E. , Mirro Amy E. , Binkley Michael M. , Guilliams Kristin P. , Lewis Josiah B. , Fellah Slim , Chen Yasheng , Hulbert Monica L. , An Hongyu , Ford Andria L. , Lee Jin‐Moo
Published: February 2022

Patients with sickle cell anemia (SCA) experience cerebral metabolic stress with an increase in oxygen extraction fraction (OEF) to compensate for reduced oxygen carrying capacity due to anemia. It remains unclear if anemia alone drives this metabolic stress. Using MRI, we collected voxel‐wise OEF measurements to test our hypothesis that OEF would be elevated in anemic controls without SCA (AC) compared to healthy controls (HC), but OEF would be even higher in SCA compared to AC. Brain MRIs (N = 159) were obtained in 120 participants (34 HC, 27 AC, 59 SCA). While hemoglobin was lower in AC versus HC (p < 0.001), hemoglobin was not different between AC and SCA cohorts (p = 0.459). Whole brain OEF was higher in AC compared to HC (p < 0.001), but lower compared to SCA (p = 0.001). Whole brain OEF remained significantly higher in SCA compared to HC (p = 0.001) while there was no longer a difference between AC versus HC (p = 0.935) in a multivariate model controlling for age and hemoglobin. OEF peaked within the border zone regions of the brain in both SCA and AC cohorts, but the volume of white matter with regionally elevated OEF in AC was smaller (1.8%) than SCA (58.0%). While infarcts colocalized within regions of elevated OEF, more SCA participants had infarcts than AC (p < 0.001). We conclude that children with SCA experience elevated OEF compared to AC and HC after controlling for the impact of anemia, suggesting that there are other pathophysiologic factors besides anemia contributing to cerebral metabolic stress in children with SCA.
Neanderthal child's occipital from Baume Moula‐Guercy (Soyons, Ardèche, France)
Authors: Richards Gary D. , Jabbour Rebecca S. , Guipert Gaspard , Defleur Alban
Published: February 2022

Objectives

This article provides an ontogenetically based comparative description of two immature occipital fragments from Baume Moula‐Guercy (MIS 5e) and examines their affinities to European and Middle Eastern Middle‐to‐Late Pleistocene (≈MIS 14–MIS ≈ 1) Homo.

Materials and methods

Description of the M‐S‐41 and M‐S‐61 occipital fragments (≈6–8 years) is based on observations of original fossils, casts, CT scans, literature descriptions, and virtual ectocranial and endocranial reconstructions. Our ontogenetically based sample represents a Preneanderthal‐Neanderthal group and a Homo sapiens group. These groups are subdivided into (1) Preneanderthals (≈MIS 14–9), Early Neanderthals (MIS 7–5e), and Late Neanderthals (MIS 5d‐3), and (2) Middle (MIS 5), Upper (MIS 3–1), and Late (MIS ≈ 1) Paleolithic H. sapiens. Measurements and developmental age determinations follow standard techniques.

Results

Based on the M‐S‐41/M‐S‐61 composite, the strongly convex upper occipital scale flattens into the vertical suprainiac fossa, as in immature Early Neanderthals. A doubled suprainiac fossa expressing a weakly developed bounding torus and pocking of the central region is typical of immature Neanderthals. The transverse torus is thickened medially, lacks significant lateral development, has a laterally placed protuberance, and is concave medially. A linear (triangular) tubercle, as opposed to an external occipital protuberance, is present. An occipital bun is absent.

Discussion

The occipital remains from Moula‐Guercy make a substantial contribution to the record of Neanderthal cranial evolution because immature Early Neanderthal occipitals are rare, fragmentary, and likely represent only two paleodemes (Krapina, La Chaise‐de‐Vouthon). The Moula‐Guercy occipital possesses characteristics well‐established in European Neanderthals by MIS 7, and it is most similar to the occipitals of other Early Neanderthals.
Remote C(sp3)−H Acylation of Amides and Cascade Cyclization via N‐Heterocyclic Carbene Organocatalysis
Authors: Li Qing‐Zhu , Zeng Rong , Fan Yang , Liu Yan‐Qing , Qi Ting , Zhang Xiang , Li Jun‐Long
Published: February 2022

The direct functionalization of inert C(sp3)−H bonds under environmentally benign catalytic conditions remains a challenging task in synthetic chemistry. Here, we report an organocatalytic remote C(sp3)−H acylation of amides and cascade cyclization through a radical‐mediated 1,5‐hydrogen atom transfer mechanism using N‐heterocyclic carbene as the catalyst. Notably, a diversity of nitrogen‐containing substrates, including simple linear aliphatic carbamates and ortho‐alkyl benzamides, can be successfully applied to this organocatalytic system. With the established protocol, over 120 examples of functionalized δ‐amino ketones and isoquinolinones with diverse substituents were easily synthesized in up to 99 % yield under mild conditions. The robustness and generality of the organocatalytic strategy were further highlighted by the successful acylation of unactivated C(sp3)−H bonds and late‐stage modification of pharmaceutical molecules. Then, the asymmetric control of the radical reaction was attempted and proven feasible by using a newly designed chiral thiazolium catalyst, and moderate enantioselectivity was obtained at the current stage. Preliminary mechanistic investigations including several control reactions, KIE experiments, and computational studies shed light on the organocatalytic radical reaction mechanism.
Palladium(II)‐Catalyzed Selective Arylation of Tertiary C−H Bonds of Cyclobutylmethyl Ketones Using Transient Directing Groups
Authors: Cheng Jin‐Tang , Xiao Li‐Jun , Qian Shao‐Qun , Zhuang Zhe , Liu An , Yu Jin‐Quan
Published: February 2022

We report the first example of selective PdII‐catalyzed tertiary C−H activation of cyclobutylmethyl ketones using a transient directing group. An electron‐deficient 2‐pyridone ligand was identified as the optimal external ligand to enable tertiary C−H activation. A variety of cyclobutylmethyl ketones bearing quaternary carbon centers was readily accessed without preinstalling internal directing groups in up to 81 % yield and >95 : 5 regioisomeric ratios of tertiary C−H arylation to β‐methylene (β‐methyl) or γ‐C−H arylation.
Reversible One‐ to Two‐ to Three‐Dimensional Transformation in CuII Coordination Polymer
Authors: Jing Yao , Yoshida Yukihiro , Huang Pingping , Kitagawa Hiroshi
Published: February 2022

A reversible transformation between 1D, 2D, and 3D is demonstrated for the first time in coordination polymers comprising CuII ions and bidentate terephthalate (BDC2−). 1D uniform chains were reversibly transformed into 2D layers with the construction of Cu‐paddlewheels by eliminating water molecules. 2D/3D reversible transformation was achieved by removing/rebinding N,N‐dimethylformamide coordinated to the paddlewheels. These dimensional transformations significantly changed chemical and physical properties such as gas sorption and magnetism. Although the uptake in open‐framework 1D and 2D Cu‐BDC was insignificant, pronounced absorption was observed for 3D Cu‐BDC. Drastic difference in magnetic behavior is consistent with their coordination structures; uniform 1D chain of CuII in 1D Cu‐BDC and 2D sheet based on CuII‐paddlewheel dimers in 2D Cu‐BDC. Ferromagnetic behavior observed in air‐exposed 3D Cu‐BDC is attributed to the 3D structure formed by the connection of 2D sheets.
Enantioselective Synthesis of (−)‐10‐Hydroxyacutuminine
Authors: Grünenfelder Denise C. , Navarro Raul , Wang Haoxuan , Fastuca Nicholas J. , Butler John R. , Reisman Sarah E.
Published: February 2022

An enantioselective synthesis of (−)‐10‐hydroxyacutuminine is reported. Central to our strategy is a photochemical [2+2] cycloaddition that forges two of the quaternary stereocenters present in the acutumine alkaloids. A subsequent retro‐aldol/Dieckmann sequence furnishes the spirocyclic cyclopentenone. Efforts to chlorinate the acutumine scaffold at C10 under heterolytic or radical deoxychlorination conditions led to the synthesis of an unexpected cyclopropane‐containing pentacycle.
Tuning Bulk O2 and Nonbonding Oxygen State for Reversible Anionic Redox Chemistry in P2‐Layered Cathodes
Authors: Li Zhenrui , Kong Weijin , Yu Yang , Zhang Jicheng , Wong Deniz , Xu Zijian , Chen Zhenhua , Schulz Christian , Bartkowiak Maciej , Liu Xiangfeng
Published: February 2022

Improving the reversibility of oxygen redox is quite significant for layered oxides cathodes in sodium‐ion batteries. Herein, we for the first time simultaneously tune bulk O2 and nonbonding oxygen state for reversible oxygen redox chemistry in P2‐Na0.67Mn0.5Fe0.5O2 through a synergy of Li2TiO3 coating and Li/Ti co‐doping. O2− is oxidized to molecular O2 and peroxide (O2)n− (n<2) during charging. Molecular O2 derived from transition metal (TM) migration is related to the superstructure ordering induced by Li doping. The synergy mechanism of Li2TiO3 coating and Li/Ti co‐doping on the two O‐redox modes is revealed. Firstly, Li2TiO3 coating restrains the surface O2 and inhibits O2 loss. Secondly, nonbonding Li−O−Na enhances the reversibility of O2−→(O2)n−. Thirdly, Ti doping strengthens the TM−O bond which fixes lattice oxygen. The cationic redox reversibility is also enhanced by Li/Ti co‐doping. The proposed insights into the oxygen redox reversibility are insightful for other oxide cathodes.
Record Aluminum Molecular Rings for Optical Limiting and Nonlinear Optics
Authors: Li Yuan , Zheng Chan , Wang San‐Tai , Liu Ya‐Jie , Fang Wei‐Hui , Zhang Jian
Published: February 2022

Crystalline cluster materials, a class of functional motif aggregations, provide a great opportunity for tuning the properties stemming from the flexible and accurate variation of inorganic and organic compositions. In this study, we demonstrate the effects of functional ligand and ring size regulation on the structures and third‐order nonlinear optical (NLO) properties. Revealed by the single‐crystal X‐ray analysis results, aluminum molecular ring expansion is achieved by 2×9 and 3×6 strategies. In terms of the given organic shells, we further tuned the aluminum molecular ring sizes from 3.0 nm to 1.7 nm. The picosecond Z‐scan measurements results revealed that the third‐order NLO performances do not only depend on the general conjugate interactions but are also related to hydrogen bonding, polarizability, and ring sizes. The large nonlinear absorption coefficient and onset prove that the observed samples are promising candidates for the field of nonlinear optics.
Single‐Vesicle Electrochemistry Reveals Sex Difference in Vesicular Storage and Release of Catecholamine
Authors: Yue Qingwei , Wang Kai , Guan Ming , Zhao Zhenwen , Li Xianchan , Yu Ping , Mao Lanqun
Published: February 2022

Quantitative measurements of sex difference in vesicle chemistry (i.e., chemical storage and release) at the single‐vesicle level are essential to understand sex differences in cognitive behaviors; however, such measurements are very challenging to conventional analytical methods. By using single‐vesicle electrochemistry, we find the duration of single exocytotic events of chromaffin cells prepared from male rats is statistically longer than that from female rats, leading to more neurotransmitter released in the male group. Further analysis reveals that a higher percentage of vesicles in the female group release part of the neurotransmitter, i.e., partial release, during exocytosis than that in male group. This sex dimorphism in neurotransmitter release in exocytosis might relate to the sex difference in the expression of voltage‐dependent calcium channels and membrane lipid composition. Our finding offers the first experimental evidence that sex dimorphism even exists in vesicle chemistry, providing a brand new viewpoint for understanding the sex dimorphism in exocytosis.
Anti‐cooperative Self‐Assembly with Maintained Emission Regulated by Conformational and Steric Effects
Authors: Helmers Ingo , Hossain Muhammad Saddam , Bäumer Nils , Wesarg Paul , Soberats Bartolome , Shimizu Linda S. , Fernández Gustavo
Published: February 2022

Herein, we present a strategy to enable a maintained emissive behavior in the self‐assembled state by enforcing an anti‐cooperative self‐assembly involving weak intermolecular dye interactions. To achieve this goal, we designed a conformationally flexible monomer unit 1 with a central 1,3‐substituted (diphenyl)urea hydrogen bonding synthon that is tethered to two BODIPY dyes featuring sterically bulky trialkoxybenzene substituents at the meso‐position. The competition between attractive forces (H‐bonding and aromatic interactions) and destabilizing effects (steric and competing conformational effects) limits the assembly, halting the supramolecular growth at the stage of small oligomers. Given the presence of weak dye–dye interactions, the emission properties of molecularly dissolved 1 are negligibly affected upon aggregation. Our findings contribute to broadening the scope of emissive supramolecular assemblies and controlled supramolecular polymerization.
Computational analysis of cross‐flow of power‐law fluids through a periodic square array of circular cylinders
Authors: Bharti Ram Prakash , Ram Ram Pravesh , Dhiman Amit Kumar
Published: February 2022

The steady flow of non‐Newtonian power‐law fluids across a periodic square array of infinitely long circular cylinders is studied numerically using an unstructured finite volume method. The local and global flow characteristics have extensively been explored by the systematic variations of the pertinent dimensionless parameters as follows: fluid volume fraction (ϕf = .70–.99), Reynolds number (Re = 1–40), and power‐law index (n = .4–1.8). Qualitatively, the dense and curved streamlines are seen with the increasing inertial forces and shear‐thinning behavior across all the fluid volume fractions. Further, the pressure coefficient over the surface of periodic cylinders is significantly influenced by the governing parameters and found to be maximum and minimum for the upstream and downstream cylinders, respectively. The individual and total drag coefficients have shown complex dependence on n, ϕf, and Re. For shear‐thinning fluids (n < 1), the pressure drag coefficient dominates over the friction drag coefficient, whereas an opposite response is seen for the shear‐thickening fluids (n > 1) except at Re = 40. Further, both individual and total drag coefficients are observed to increase and decrease in the ranges of ϕf of .70–.90 and .92–.99, respectively, with increasing n. The strong interactions between the periodic cylinders, at smaller ϕf, diminish with a corresponding increase in ϕf. In addition, simple predictive correlations for the pressure, friction, and total drag coefficients have been developed to gain further physical insights into the detailed flow kinematics. Finally, the present findings display a good agreement with the available literature.
Influence of different mixing sequence on UHMW‐EPDM based thermoplastic vulcanizates: Mechanical, rheological and morphological characteristics
Authors: Bhattacharya Asit Baran , Das Mithun , Sreethu T. K. , Maji Purbasha , Naskar Kinsuk
Published: February 2022

An important factor for the preparation of thermoplastic vulcanizates (TPVs) is the mixing sequence or technique as it is controlling the product quality and production rate. The effect of different routes of mixing sequences on the mechanical properties and rheological properties have been studied. Four different types of mixing sequences have been pursued and ultra‐high molecular weight EPDM (UHMW‐EPDM) master batch technique has shown maximum prospect over the melt blending method. Co‐agent master‐batch sample showed optimum balance between TS and %EB over the other master‐batch samples. Melt blending technique shows moderate properties for all cases. Rheological data follows the same trend as observed for the mechanical properties. Crosslink density also found the highest for the co‐agent master‐batch sample and co‐agent/peroxide master‐batch sample over the other two samples. Cryo‐fractured and etched TPV samples were prepared and examined in FE‐SEM. Co‐agent master‐batch sample shows the droplet type morphology. This new type of UHMW‐EPDM based TPV with co‐agent/rubber master‐batch mixing technique leads to superior physico‐mechanical properties over the other mixing techniques. These newly established TPVs can be used as various injection molded parts, esthetic seals/strips and 2K‐molds for the automotive applications.
Differential N‐ and O‐glycosylation signatures of HIV‐1 Gag virus‐like particles and coproduced extracellular vesicles
Authors: Lavado‐García Jesús , Zhang Tao , Cervera Laura , Gòdia Francesc , Wuhrer Manfred
Published: February 2022

Human immunodeficiency virus 1 (HIV‐1) virus‐like particles (VLPs) are nanostructures derived from the self‐assembly and cell budding of Gag polyprotein. Mimicking the native structure of the virus and being noninfectious, they represent promising candidates for the development of new vaccines as they elicit a strong immune response. In addition to this, the bounding membrane can be functionalized with exogenous antigens to target different diseases. Protein glycosylation depends strictly on the production platform and expression system used and the displayed glycosylation patterns may influence downstream processing as well as the immune response. One of the main challenges for the development of Gag VLP production bioprocess is the separation of VLPs and coproduced extracellular vesicles (EVs). In this study, porous graphitized carbon separation method coupled with mass spectrometry was used to characterize the N‐ and O‐ glycosylation profiles of Gag VLPs produced in HEK293 cells. We identified differential glycan signatures between VLPs and EVs that could pave the way for further separation and purification strategies to optimize downstream processing and move forward in VLP‐based vaccine production technology.
Role of histidine decarboxylase gene in the pathogenesis of Tourette syndrome
Authors: Xu Lulu , Zhang Cheng , Zhong Meixiang , Che Fengyuan , Guan Chengcheng , Zheng Xueping , Liu Shiguo
Published: February 2022

Tourette syndrome (TS) is caused by complex genetic and environmental factors and is characterized by tics. Histidine decarboxylase (HDC) mutation is a rare genetic cause with high penetrance in patients with TS. HDC‐knockout (KO) mice have similar behavioral and neurochemical abnormalities as patients with TS. Therefore, HDC‐KO mice are considered a valuable TS pathophysiological model as it reveals the underlying pathological mechanisms that cannot be obtained from patients with TS, thus advancing the development of treatment strategies for TS and other tic disorders. This review summarizes some of the recent research hotspots and progress in HDC‐KO mice, aiming to deepen our understanding of brain mechanisms relevant to TS. Furthermore, we encapsulate the possible brain nerve cell changes in HDC‐KO mice and their potential roles in TS to provide multiple directions for the future research on tics.
Immobilization of the Aspartate Ammonia‐Lyase from Pseudomonas fluorescens R124 on Magnetic Nanoparticles: Characterization and Kinetics
Authors: Csuka Pál , Molnár Zsófia , Tóth Veronika , Imarah Ali Obaid , Balogh‐Weiser Diána , Vértessy Beáta G. , Poppe László
Published: February 2022

Aspartate ammonia‐lyases (AALs) catalyze the non‐oxidative elimination of ammonia from l‐aspartate to give fumarate and ammonia. In this work the AAL coding gene from Pseudomonas fluorescens R124 was identified, isolated, and cloned into the pET‐15b expression vector and expressed in E. coli. The purified enzyme (PfAAL) showed optimal activity at pH 8.8, Michaelis‐Menten kinetics in the ammonia elimination from l‐aspartate, and no strong dependence on divalent metal ions for its activity. The purified PfAAL was covalently immobilized on epoxy‐functionalized magnetic nanoparticles (MNP), and effective kinetics of the immobilized PfAAL‐MNP was compared to the native solution form. Glycerol addition significantly enhanced the storability of PfAAL‐MNP. Inhibiting effect of the growing viscosity (modulated by addition of glycerol or glucose) on the enzymatic activity was observed for the native and immobilized form of PfAAL, as previously described for other free enzymes. The storage stability and recyclability of PfAAL‐MNP is promising for further biocatalytic applications.
Mapping the Conformational Landscape of the Neutral Network of RNA Sequences That Connect Two Functional Distinctly Different Ribozymes
Authors: Knezic Bozana , Keyhani‐Goldau Sara , Schwalbe Harald
Published: February 2022

During evolution of an RNA world, the development of enzymatic function was essential. Such enzymatic function was linked to RNA sequences capable of adopting specific RNA folds that possess catalytic pockets to promote catalysis. Within this primordial RNA world, initially evolved self‐replicating ribozymes presumably mutated to ribozymes with new functions. Schultes and Bartel (Science 2000, 289, 448–452) investigated such conversion from one ribozyme to a new ribozyme with distinctly different catalytic functions. Within a neutral network that linked these two prototype ribozymes, a single RNA chain could be identified that exhibited both enzymatic functions. As commented by Schultes and Bartel, this system possessing one sequence with two enzymatic functions serves as a paradigm for an evolutionary system that allows neutral drifts by stepwise mutation from one ribozyme into a different ribozyme without loss of intermittent function. Here, we investigated this complex functional diversification of ancestral ribozymes by analyzing several RNA sequences within this neutral network between two ribozymes with class III ligase activity and with self‐cleavage reactivity. We utilized rapid RNA sample preparation for NMR spectroscopic studies together with SHAPE analysis and in‐line probing to characterize secondary structure changes within the neutral network. Our investigations allowed delineation of the secondary structure space and by comparison with the previously determined catalytic function allowed correlation of the structure‐function relation of ribozyme function in this neutral network.
Predicting mortality in nonsurgical patients before cannulation for veno‐arterial extracorporeal life support: Development and validation of the LACT‐8 score
Authors: Hillerson Dustin , Whiteside Hoyle L. , Dugan Adam J. , Coots Riley D. , Tribble Thomas A. , Abdel‐Latif Ahmed , Ogunbayo Gbolahan O. , Duncan Meredith S. , Gupta Vedant A.
Published: February 2022

Objectives

We sought to derive and validate a model to predict inpatient mortality after veno‐arterial extracorporeal life support (VA‐ECLS) based on readily available, precannulation clinical data.

Background

Refractory cardiogenic shock supported by VA‐ECLS is associated with high morbidity and mortality.

Methods

VA‐ECLS cases at our institution from January 2014 through July 2019 were retrospectively reviewed. Exclusion criteria were cannulation: (1) at another institution; (2) for primary surgical indication; or (3) for extracorporeal cardiopulmonary resuscitation. Multivariable logistic regression compared those with and without inpatient mortality. Multiple imputation was performed and optimism‐adjusted area under the curve (oAUC) values were computed.

Results

VA‐ECLS cases from August 2019 through November 2020 were identified as a validation cohort. In the derivation cohort (n = 135), the final model included Lactate (mmol/L), hemoglobin (g/dl; Anemia), Coma (Glasgow Coma Scale [GCS] < 8) and resusciTATEd cardiac arrest (LACTATE score; oAUC = 0.760). In the validation cohort (n = 30, LACTATE showed similar predictability [AUC = 0.710]). A simplified (LACT‐8) score was derived by dichotomizing lactate (>8) and hemoglobin (<8) and summing together the number of components for each patient. LACT‐8 performed similarly (derivation, oAUC = 0.724; validation, AUC = 0.725). In the derivation cohort, both scores outperformed SAVE (oAUC = 0.568) and SOFA (oAUC = 0.699) scores. A LACT‐8 ≥ 3 had a specificity for mortality of 97.9% and 92.9%, in the derivation and validation cohorts, respectively.

Conclusions

The LACT‐8 score can predict inpatient mortality prior to before cannulation for VA‐ECLS. LACT‐8 can be implemented utilizing clinical data without the need for an online calculator.
Continuous atrial pressure monitoring via steerable guide catheter in transcatheter mitral and tricuspid edge‐to‐edge repair
Authors: Rottländer Dennis , Beucher Harald , Ghaddioui Karim Al , Boekstegers Peter
Published: February 2022

Transcatheter edge‐to‐edge repair (TEER) has emerged to address severe mitral and tricuspid valve regurgitation in patients who are at high perioperative risk for open‐heart surgery. No clinical data is available for continuous left and right atrial pressure monitoring using the steerable guiding catheter (SGC) during TEER. In a prospective single‐center study, 40 patients with severe mitral (n = 20) or tricuspid (n = 20) regurgitation underwent TEER with the registration of atrial pressure via the SGC. All patients had successful TEER using the PASCAL Ace repair system, while atrial pressure was monitored continuously via the SGC. Simultaneous right or left atrial pressure monitoring via the SGC and a pigtail catheter during mitral and tricuspid TEER showed excellent reliability for SGC pressure registration. While for mitral TEER the beneficial effects of continuous atrial pressure monitoring are well known, we further evaluated the outcome of patients with tricuspid TEER. Echocardiographic and clinical results after tricuspid TEER showed a reduction of quantitative echocardiographic tricuspid regurgitation parameters and improved New York Heart Association classification after 3‐month follow‐up. Also, qualitative tricuspid valve assessment showed improved tricuspid regurgitation classification postimplantation and at 3‐month follow‐up. Furthermore, right atrial pressure was reduced by 37.6% and mean right atrial pressure by 30.6% after successful tricuspid TEER using the PASCAL Ace device. Continuous atrial pressure monitoring using the SGC of the PASCAL Ace repair system is reliable during mitral and tricuspid TEER. Furthermore, successful tricuspid TEER leads to reduced right atrial pressure.
The relevance of tricuspid regurgitation in patients undergoing percutaneous treatment of mitral regurgitation
Authors: Brunner Stephanie , Wolfrum Mathias , Moccetti Federico , Stämpfli Simon F. , Attinger‐Toller Adrian , Bossard Matthias , Matt Peter , Cuculi Florim , Kobza Richard , Toggweiler Stefan
Published: February 2022

Objectives

 Investigate the impact of concomitant tricuspid regurgitation (TR) on clinical outcomes during long‐term follow‐up in patients undergoing percutaneous treatment of mitral regurgitation (MR) with the MitraClip system.

Background

Patients undergoing mitral repair using the MitraClip frequently present with concomitant TR. It is uncertain how the presence of TR impacts the long‐term outcomes of such patients.

Methods

We analyzed consecutive patients with MitraClip implantation from the prospective MitraSwiss registry. Endpoints were all‐cause mortality, hospitalization for heart failure, and the composite endpoint of the two.

Results

We enrolled 177 patients (mean age 76 ± 9 years, 37% female). Acute procedural success was achieved in 149 (84%). Concomitant moderate or severe TR was present in 31% at baseline and 32% before discharge. After a median follow‐up of 1103 days (IQR: 555–1766 days), 70 (40%) of patients had died, and 34 (19%) were hospitalized for heart failure. In multivariable analysis, TR at baseline was associated with an increase in all‐cause mortality (HR: 2.34, 95% CI: 1.36–4.03, p < 0.01), hospitalization for heart failure (HR: 3.19, 95% CI: 1.37–7.41, p = 0.01), and the composite endpoint (HR: 2.00, 95% CI: 1.19−3.36, p = 0.01).

Conclusion

Despite treatment of MR, TR did not improve in most patients. The presence of relevant TR at baseline was associated with reduced survival and higher rates of hospitalization for heart failure. More research is needed to understand the causal role of TR in such patients and to investigate if simultaneous treatment of concomitant TR may improve prognosis in patients undergoing percutaneous treatment of MR.
Case of atypical disseminated herpes zoster in a patient with COVID‐19: A diagnostic challenge in COVID era
Authors: Mohaghegh Fatemeh , Hatami Parvaneh , Aryanian Zeinab
Published: February 2022

Herpes Zoster caused by reactivation of latent Varicella–Zoster virus (VZV). The rare disseminated form of it occurred mainly in immunocompromised patients. We hereby present the first case of atypical disseminated herpes zoster in a 54‐year‐old woman admitted with serious COVID. In this case, disseminated herpes zoster developed by purpuric lesions mimicking vasculitis and cutaneous drug reaction. Hence, this case serves as a reminder for considering atypical presentations of cutaneous disorders in immunocompromised patients, especially those affected with severe COVID.
Clinical impact and benefits of a simultaneous cardio‐pulmonary rehabilitation in a COVID‐19‐infected patient following cardiac arrest: A case report
Authors: Lee Mirim , Lee Jeong Jae , Ko Jun young , Kim Yong Kyun , Lee Seungbok
Published: February 2022

Since the advent of the pandemic, cardio‐pulmonary rehabilitation (CR) has been shown to be an effective treatment. However, there are no studies showing data to substantiate its simultaneous application. A 62‐year‐old man was resuscitated for asystole during the work‐up after presenting with a 2‐day history of difficulty breathing. PCR test was positive for COVID‐19. He was intubated and admitted to a negative pressure zone. Symptoms improved in response to acute treatment. Following extubation, respiratory distress persisted, and CR was implemented. Clinical indicators of cardiopulmonary function improved resulting in a successful return to community participation. The decline in cardiopulmonary function has been on the rise among COVID‐19 survivors. The simultaneous application of CR treatment in our patient resulted in improved clinical indicators of cardiopulmonary function. The patient regained full function for independent community participation.
Preprocedural imaging for transcatheter mitral valve‐in‐valve replacement: Planning makes perfect
Authors: Van De Bruaene Alexander , De Buck Stijn , Verbrugghe Peter , Dubois Christophe
Published: February 2022

Transcatheter mitral valve‐in‐valve replacement (TMViVR) in degenerated bioprostheses or valvular rings shows promise as an alternative to surgical MVR in selected high‐risk patients. However, these procedures are particularly challenging given the complex anatomy of the mitral valve apparatus and the surrounding structures, potentially causing LV outflow tract obstruction (LVOTO). Preprocedural planning with virtual implantation and planimetric estimation of the neo‐LVOT at end‐systole is crucial for improving procedural results. In this case, we also include a dynamic evaluation of the neo‐LVOT and implement virtual reality imaging for immersive assessment of the implanted valve.
Catalyst‐Free Intermolecular Sulfonyl/Fluoromethyl Heteroarylation of Vinyl Ethers via Visible‐Light‐Induced Charge Transfer
Authors: Long Tianyu , Pan Shiwei , Zhu Shengqing , Chu Lingling
Published: February 2022

We report a visible‐light‐induced three‐component sulfonyl‐heteroarylation of vinyl ethers with sulfinates and five‐membered heteroaryl chlorides. This protocol proceeds via electron‐donor‐acceptor (EDA) complexes between sulfinates and heteroaryl chlorides, giving β‐sulfonyl alkyl five‐membered heteroarenes with high efficiency and excellent regioselectivity under mild and catalyst‐free conditions. Utilization of CF3SO2Na or CF2HSO2Na as coupling partners further achieves three‐component fluoromethyl‐arylation of vinyl ethers, furnishing a series of valuable CF3/CF2H‐incorporated alkyl heterocycles under mild conditions.
Heterodinuclear Mg(II)M(II) (M=Cr, Mn, Fe, Co, Ni, Cu and Zn) Complexes for the Ring Opening Copolymerization of Carbon Dioxide/Epoxide and Anhydride/Epoxide
Authors: Reis Natalia V. , Deacy Arron C. , Rosetto Gloria , Durr Christopher B. , Williams Charlotte K.
Published: February 2022

The catalysed ring opening copolymerizations (ROCOP) of carbon dioxide/epoxide or anhydride/epoxide are controlled polymerizations that access useful polycarbonates and polyesters. Here, a systematic investigation of a series of heterodinuclear Mg(II)M(II) complexes reveals which metal combinations are most effective. The complexes combine different first row transition metals (M(II)) from Cr(II) to Zn(II), with Mg(II); all complexes are coordinated by the same macrocyclic ancillary ligand and by two acetate co‐ligands. The complex syntheses and characterization data, as well as the polymerization data, for both carbon dioxide/cyclohexene oxide (CHO) and endo‐norbornene anhydride (NA)/cyclohexene oxide, are reported. The fastest catalyst for both polymerizations is Mg(II)Co(II) which shows propagation rate constants (kp) of 34.7 mM−1 s−1 (CO2) and 75.3 mM−1 s−1 (NA) (100 °C). The Mg(II)Fe(II) catalyst also shows excellent performances with equivalent rates for CO2/CHO ROCOP (kp=34.7 mM−1 s−1) and may be preferable in terms of metallic abundance, low cost and low toxicity. Polymerization kinetics analyses reveal that the two lead catalysts show overall second order rate laws, with zeroth order dependencies in CO2 or anhydride concentrations and first order dependencies in both catalyst and epoxide concentrations. Compared to the homodinuclear Mg(II)Mg(II) complex, nearly all the transition metal heterodinuclear complexes show synergic rate enhancements whilst maintaining high selectivity and polymerization control. These findings are relevant to the future design and optimization of copolymerization catalysts and should stimulate broader investigations of synergic heterodinuclear main group/transition metal catalysts.
Charge Carrier Transport Mechanism in Ta2O5, TaON, and Ta3N5 Studied by Applying Polaron Hopping and Bandlike Models
Authors: Zhao Qianyu , Cui Mengsi , Liu Taifeng
Published: February 2022

TaON and Ta3N5 are considered promising materials for photocatalytic and photoelectrochemical water splitting. In contrast, their counterpart Ta2O5 does not exhibit good photocatalytic performance. This may be explained with the different charge carrier transport mechanisms in these materials, which are not well understood yet. Herein, we investigate the charge transport properties in Ta2O5, TaON, and Ta3N5 by polaron hopping and bandlike models. First, the polaron binding energies were calculated to evaluate whether the small polaron occurs in these materials. Then we performed calculations to localize the excess carriers as small polarons using a hybrid density functional. We find that the small polaron hopping is the charge transfer mechanism in Ta2O5, whereas our calculations indicate that this mechanism may not occur in TaON and Ta3N5. We also investigated the bandlike model mechanism by calculating the charge carrier mobility of these materials using the effective mass approximation, but the calculated mobility is not consistent with experimental results. This study is a first step towards understanding charge transport in oxynitrides and nitrides and furthermore establishes a simple rule to determine whether a small polaron occurs in a material.
Genetic architecture of yield‐component traits in the new perennial grain crop, intermediate wheatgrass
Authors: Altendorf Kayla Rae , DeHaan Lee R. , Anderson James
Published: February 2022

Intermediate wheatgrass [Thinopyrum intermedium (Host) Barkworth & D.R. Dewey] (IWG) is a perennial, cool‐season grass species currently undergoing direct domestication as one of the first perennial grain crops. To domesticate and improve this obligately outcrossing allohexaploid (2n = 6x = 42), breeders are using both phenotypic‐ and genomic‐assisted recurrent selection methodologies. Thus far, efforts have focused primarily on improving domestication traits and yield, but breeders are limited by the relatively narrow understanding of the genetic control of these traits. An IWG nested association mapping (NAM) population with 1,168 F1 progeny from 10 families was grown in four unique growing environments (St. Paul, MN, and Salina, KS, in 2017 and 2018) and evaluated for a series of 11 yield‐component traits. Using a population‐specific genetic map and 8,003 single‐nucleotide polymorphism (SNP) markers, we used both linkage mapping (LM) and genome‐wide association study (GWAS) to dissect the genetic control of a series of yield‐component traits. We identified 20 significant markers in GWAS and 28 in LM that were detected in at least two environments, several of which were shared across traits. The QTL regions on chromosomes 5 and 9 were significant for eight of 11 traits, and many were detected across multiple analysis methods. The results described herein provide additional resources for incorporating QTL as fixed effects in routine genomic selection pipelines to expedite the gains from selection for yield in this new perennial grain crop.
Versatile Chemical Recycling Strategies: Value‐Added Chemicals from Polyester and Polycarbonate Waste
Authors: Payne Jack M. , Kamran Muhammad , Davidson Matthew G. , Jones Matthew D.
Published: February 2022

ZnII‐complexes bearing half‐salan ligands were exploited in the mild and selective chemical upcycling of various commercial polyesters and polycarbonates. Remarkably, we report the first example of discrete metal‐mediated poly(bisphenol A carbonate) (BPA‐PC) methanolysis being appreciably active at room temperature. Indeed, Zn(2)2 and Zn(2)Et achieved complete BPA‐PC consumption within 12–18 mins in 2‐Me‐THF, noting high bisphenol A (BPA) yields (SBPA=85–91 %) within 2–4 h. Further kinetic analysis found such catalysts to possess kapp values of 0.28±0.040 and 0.47±0.049 min−1 respectively at 4 wt%, the highest reported to date. A completely circular upcycling approach to plastic waste was demonstrated through the production of several renewable poly(ester‐amide)s (PEAs), based on a terephthalamide monomer derived from bottle‐grade poly(ethylene terephthalate) (PET), which exhibited excellent thermal properties.
Inhibition of renal fibrosis with a human CXCL9‐derived glycosaminoglycan‐binding peptide
Authors: Poosti Fariba , Soebadi Mohammad Ayodhia , Crijns Helena , De Zutter Alexandra , Metzemaekers Mieke , Berghmans Nele , Vanheule Vincent , Albersen Maarten , Opdenakker Ghislain , Van Damme Jo , Sprangers Ben , Proost Paul , Struyf Sofie
Published: February 2022

Objectives

Renal fibrosis accompanies all chronic kidney disorders, ultimately leading to end‐stage kidney disease and the need for dialysis or even renal replacement. As such, renal fibrosis poses a major threat to global health and the search for effective therapeutic strategies to prevent or treat fibrosis is highly needed. We evaluated the applicability of a highly positively charged human peptide derived from the COOH‐terminal domain of the chemokine CXCL9, namely CXCL9(74–103), for therapeutic intervention. Because of its high density of net positive charges at physiological pH, CXCL9(74–103) competes with full‐length chemokines for glycosaminoglycan (GAG) binding. Consequently, CXCL9(74–103) prevents recruitment of inflammatory leucocytes to sites of inflammation.

Methods

CXCL9(74–103) was chemically synthesised and tested in vitro for anti‐fibrotic properties on human fibroblasts and in vivo in the unilateral ureteral obstruction (UUO) mouse model.

Results

CXCL9(74–103) significantly reduced the mRNA and/or protein expression of connective tissue growth factor (CTGF), alpha‐smooth muscle actin (α‐SMA) and collagen III by transforming growth factor (TGF)‐β1‐stimulated human fibroblasts. In addition, administration of CXCL9(74–103) inhibited fibroblast migration towards platelet‐derived growth factor (PDGF), without affecting cell viability. In the UUO model, CXCL9(74–103) treatment significantly decreased renal α‐SMA, vimentin, and fibronectin mRNA and protein expression. Compared with vehicle, CXCL9(74–103) attenuated mRNA expression of TGF‐β1 and the inflammatory markers/mediators MMP‐9, F4/80, CCL2, IL‐6 and TNF‐α. Finally, CXCL9(74–103) treatment resulted in reduced influx of leucocytes in the UUO model and preserved tubular morphology. The anti‐fibrotic and anti‐inflammatory effects of CXCL9(74–103) were mediated by competition with chemokines and growth factors for GAG binding.

Conclusions

Our findings provide a scientific rationale for targeting GAG–protein interactions in renal fibrotic disease.
Landscape heterogeneity filters functional traits of rice arthropods in tropical agroecosystems
Authors: Dominik Christophe , Seppelt Ralf , Horgan Finbarr G. , Settele Josef , Václavík Tomáš
Published: February 2022

Biological control services of agroecosystems depend on the functional diversity of species traits. However, the relationship between arthropod traits and landscape heterogeneity is still poorly understood, especially in tropical rice agroecosystems, which harbor a high diversity of often specialized species. We investigated how landscape heterogeneity, measured by three metrics of landscape composition and configuration, influenced body size, functional group composition, dispersal ability, and vertical distribution of rice arthropods in the Philippines. We found that landscape composition and configuration acted to filter arthropod traits in tropical rice agroecosystems. Landscape diversity and rice habitat fragmentation were the two main gradients influencing rice‐arthropod traits, indicating that different rice arthropods have distinct habitat requirements. Whereas small parasitoids and species mostly present in the rice canopy were favored in landscapes with high compositional heterogeneity, predators and medium‐sized species occupying the base of the rice plant, including planthoppers, mostly occurred in highly fragmented rice habitats. We demonstrate the importance of landscape heterogeneity as an ecological filter for rice arthropods, identifying how the different components of landscape heterogeneity selected for or against specific functional traits. However, the contrasting effects of landscape parameters on different groups of natural enemies indicate that not all beneficial rice arthropods can be promoted at the same time when using a single land management strategy. Increasing compositional heterogeneity in rice landscapes can promote parasitoids but may also negatively affect predators. Future research should focus on identifying trade‐offs between fragmented rice habitats and structurally diverse landscapes to maximize the presence of multiple groups of beneficial arthropods.
Azoliums and Ag(I)‐N‐Heterocyclic Carbene Thioglycosides: Synthesis, Reactivity and Bioactivity
Authors: Ryzhakov Dmytro , Beillard Audrey , Le Bideau Franck , Al‐Shuaeeb Riyadh Ahmed Atto , Alami Mouad , Bantreil Xavier , Bonnemoy Aurore , Gautier Arnaud , Lamaty Frédéric , Messaoudi Samir
Published: February 2022

A versatile protocol for the synthesis of azolium thioglycosides is reported. This protocol is based on a PdG3‐catalyzed Migita cross‐coupling between p‐di‐iodo azoliums and protected or unprotected β‐1‐thioglucose partners. Moreover, a solvent‐free mechanochemistry approach was developed as a unique access to the corresponding Ag(I)‐N‐heterocyclic carbene thioglycosides. Finally, chemical reactivity and antiproliferative bioactivity were examined with azoliums and Ag(I)‐NHC thioglycosides. This study demonstrates a promising potential of these newly synthesized carbohydrate‐based N‐heterocyclic derivatives.
Who's a yea‐sayer? Habitual trust and affirmative response behaviour
Authors: Posten Ann‐Christin , Steinmetz Janina
Published: February 2022

We test the hypothesis that people who habitually trust others respond more affirmatively to questions (i.e. acquiescence). Six studies explore whether people's habitual tendency to trust others translates into a general acquiescent response bias. By re‐analysing large‐scale cross‐country data, Study 1 shows that participants’ level of habitual trust predicts agreement across multiple and diverse concepts. Studies 2a and 2b show that habitual trust predicts acquiescent responding in classic psychological questionnaires. Habitual trust likewise predicts behavioural acquiescence, such as an agreement to assign monetary awards to others (Study 3) and staying with the suggested default option in a real choice paradigm (Study 4). Furthermore, the relation between habitual trust and acquiescent responding holds across different communication contexts (Study 5). These results imply that habitual trust predicts how individuals respond to questionnaire items that are used across a variety of research domains.