bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bioinspired and Ligand‐Regulated Unnatural Prenylation and Geranylation of Oxindoles with Isoprene under Pd Catalysis
Authors: Zhao Chao‐Yang , Liu Ying‐Ying , Zhang Xiang‐Xin , He Gu‐Cheng , Liu Heng , Ji Ding‐Wei , Hu Yan‐Cheng , Chen Qing‐An 
Published: June 2022

AbstractIn nature, prenylation and geranylation are two important metabolic processes for the creation of hemiterpenoids and monoterpenoids under enzyme catalysis. Herein, we have demonstrated bioinspired unnatural prenylation and geranylation of oxindoles using the basic industrial feedstock isoprene through ligand regulation under Pd catalysis. Pentenylated oxindoles (with C5 added) were attained with high selectivity when using a bisphosphine ligand, whereas upon switching to a monophosphine ligand, selectivity toward geranylated oxindoles (with C10 added) was achieved. Moreover, the head‐to‐head product could be further isomerized to an internal skipped diene under Pd−H catalysis. No stoichiometric by‐product was formed in the process.
Isolierung eines Arsendiradikaloids mit einem zyklischen C2As2‐Gerüst
Authors: Steffenfauseweh Henric , Vishnevskiy Yury V. , Neumann Beate , Stammler Hans‐Georg , Andrada Diego M. , Ghadwal Rajendra S. 
Published: June 2022

AbstractIn diesem Artikel berichten wir über die Synthese, Charakterisierung und Reaktivitätsstudien des ersten zyklischen C2As2‐Diradikaloids {(IPr)CAs}2 (6) (IPr = C{N(Dipp)CH}2; Dipp = 2,6‐iPr2C6H3). Die Umsetzung von (IPr)CH2 (1) mit AsCl3 ergibt das Lewis‐Addukt {(IPr)CH2}AsCl3 (2). Verbindung 2 geht schrittweise eine Dehydrochlorierung ein, die über {(IPr)CH}AsCl2 (3) zu {(IPr)CAsCl}2 (5 a) oder [{(IPr)CAs}2Cl]OTf (5 b) führt. Die Reduktion von 5 a (oder 5 b) mit Magnesiumspänen ergibt 6 als roten kristallinen Feststoff in 90 %iger Ausbeute. Verbindung 6, die einen planaren C2As2‐Ring aufweist, ist diamagnetisch und zeigt gut aufgelöste NMR‐Signale. DFT‐Berechnungen zeigen einen Singulett‐Grundzustand für 6 mit einer kleinen Singulett‐Triplett‐Energielücke von 8.7 kcal mol−1. Der diradikalische Charakter von 6 beträgt 20% (CASSCF, Complete Active Space Self Consistent Field) und 28% (DFT). Die Reaktionen von 6 mit (PhSe)2 bzw. Fe2(CO)9 führen zur Bildung von {(IPr)CAs(SePh)}2 (7) bzw. {(IPr)CAs}2Fe(CO)4 (8).
Isolation of an Arsenic Diradicaloid with a Cyclic C2As2‐Core
Authors: Steffenfauseweh Henric , Vishnevskiy Yury V. , Neumann Beate , Stammler Hans‐Georg , Andrada Diego M. , Ghadwal Rajendra S. 
Published: June 2022

AbstractHerein, we report on the synthesis, characterization, and reactivity studies of the first cyclic C2As2‐diradicaloid {(IPr)CAs}2 (6) (IPr = C{N(Dipp)CH}2; Dipp = 2,6‐iPr2C6H3). Treatment of (IPr)CH2 (1) with AsCl3 affords the Lewis adduct {(IPr)CH2}AsCl3 (2). Compound 2 undergoes stepwise dehydrochlorination to yield {(IPr)CH}AsCl2 (3) and {(IPr)CAsCl}2 (5 a) or [{(IPr)CAs}2Cl]OTf (5 b). Reduction of 5 a (or 5 b) with magnesium turnings gives 6 as a red crystalline solid in 90% yield. Compound 6 featuring a planar C2As2 ring is diamagnetic and exhibits well resolved NMR signals. DFT calculations reveal a singlet ground state for 6 with a small singlet‐triplet energy gap of 8.7 kcal mol−1. The diradical character of 6 amounts to 20% (CASSCF, complete active space self consistent field) and 28% (DFT). Treatments of 6 with (PhSe)2 and Fe2(CO)9 give rise to {(IPr)CAs(SePh)}2 (7) and {(IPr)CAs}2Fe(CO)4 (8), respectively.
Effects of different polyolefin copolymers on properties of melt mixed polypropylene blends
Authors: Doan Thi Thu Loan , Müller Michael Thomas , Nguyen Hoang M. 
Published: June 2022

AbstractPolypropylene (PP) is an affordable plastic commodity but lacks massive use in engineering applications given its limited mechanical properties including significantly low impact strength. In this work, three polyolefin‐based copolymers including ethylene‐octene random block (Engage, E), ethylene‐octene multi‐block (Infuse, I), and ethylene‐propylene copolymer (Versify, V) were blended with PP. It was found that the V copolymer was miscible while the rests were immiscible in the PP matrix. Mechanical testings indicated that the addition of the 20% E and 20% I copolymers significantly enhanced the impact toughness of PP up to 83% and 108% at −20°C, respectively. At a higher temperature such as 25°C, the impact toughness of the PP/E20 and PP/I20 were 400 and 571%, respectively. The enhancement of the PP impact toughness was governed by the particle size of the added immiscible copolymers. Experimental results also revealed that the good compatibility between PP and copolymers has an insignificant influence on the mechanical properties of PP while the essence of added copolymer plays a key role instead. The findings from this work provide significant insights into the design of PP‐based products with desirable properties to satisfy requirements demanded by engineering applications.
Medication use during pregnancy among women with congenital physical disabilities
Authors: García Michelle Huezo , Petersen Julie M. , Parker Samantha E. , Rubenstein Eric , Werler Martha M. 
Published: June 2022

AbstractBackgroundMedication use during pregnancy is common, with up to 90% of pregnant women taking at least one medication. Women with congenital physical disabilities often report co‐occurring conditions during pregnancy that may warrant pharmaceutical treatment, however, research is limited. We aim to describe medication use during pregnancy including: pain, psychotropic, and antibacterial medication, among women with and without congenital physical disabilities.MethodsWe used data from the Slone Birth Defects Study (1976–2015), a case–control study that collected information on pre‐pregnancy health conditions and exposures among participating mothers. Women with congenital physical disabilities (n = 132) included women with spina bifida, cerebral palsy, muscular dystrophy, limb deficiencies, and other skeletal/connective tissue conditions and were matched by interview year and study site to women without congenital physical disabilities (n = 528). Proportions and difference in proportions for each medication were compared between groups. Simple proportions were also calculated for duration and multiple medication use variables.ResultsWomen with congenital physical disabilities more frequently reported use of pain (acetaminophen and opioids), psychotropic (antidepressants), and antibacterial medications during pregnancy. Women with congenital physical disabilities used pain and psychotropic medications for longer, frequent durations, and more frequently reported haven taken multiple medications during pregnancy.ConclusionWomen with congenital physical disabilities report higher medication use during pregnancy compared to women without physical disabilities. Patterns may be attributable to co‐occurring conditions or increased risk of pregnancy complications in this population. Further research is needed to describe the patterns of medication use for clinical decisions regarding treatment of pregnant women with disabilities.
Lifestyle treatment in women with polycystic ovary syndrome: predictors of weight loss and dropout
Authors: Jiskoot Geranne , Dietz de Loos Alexandra , Timman Reinier , Beerthuizen Annemerle , Laven Joop , Busschbach Jan 
Published: June 2022

AbstractBackgroundPolycystic ovary syndrome (PCOS) affects 5%–10% of women in their reproductive years. Most women with PCOS struggle with obesity during their entire life. Knowing which determinants contribute to a successful lifestyle change is important to optimize treatment options for women with PCOS.ObjectiveThis analysis of secondary outcome measures aimed to determine factors of ≥5% weight loss and dropout in all arms of the study and separately in the lifestyle intervention (LI) and control (care as usual [CAU]) groups.Study designWomen diagnosed with PCOS (N = 183) and a Body Mass Index (BMI) above 25 kg/m2 were included. Participants were assigned to (1) 20 lifestyle sessions involving cognitive behavioral therapy (CBT), (2) 20 lifestyle sessions involving CBT with additional short message service (SMS), or (3) to control (CAU). A generalized linear regression was performed to identify determinants of ≥5% weight loss. Logistic regression was performed to identify determinants of dropout. All models were corrected by including baseline weight as a covariate.ResultsLI (OR 4.906, p = .001) was associated with ≥5% weight loss, while higher depression scores (OR 0.549, p = .013) had a negative association. Restraint eating was a positive factor for ≥5% weight loss in LI but a negative in CAU. Higher baseline weight (OR 1.033, p = .006), LI with SMS (OR 4.424, p = .002), and higher levels of androstenedione (OR 1.167, p = .026) were associated with dropout.ConclusionsDepression and eating behavior were associated with ≥5% weight loss. Women with PCOS should be screened for depression and eating behavior before a LI.
Unraveling the mystery of white matter in depression: A translational perspective on recent advances
Authors: Abraham Mate , Mundorf Annakarina , Brodmann Katja , Freund Nadja 
Published: June 2022

AbstractBackgroundNumerous cortical and subcortical structures have been studied extensively concerning alterations of their integrity as well as their neurotransmitters in depression. However, connections between these structures have received considerably less attention.ObjectiveThis systematic review presents results from recent neuroimaging as well as neuropathologic studies conducted on humans and other mammals. It aims to provide evidence for impaired white matter integrity in individuals expressing a depressive phenotype.MethodsA systematic database search in accordance with the PRISMA guidelines was conducted to identify imaging and postmortem studies conducted on humans with a diagnosis of major depressive disorder, as well as on rodents and primates subjected to an animal model of depression.ResultsAlterations are especially apparent in frontal gyri, as well as in structures establishing interhemispheric connectivity between frontal regions. Translational neuropathological findings point to alterations in oligodendrocyte density and morphology, as well as to alterations in the expression of genes related to myelin synthesis. An important role of early life adversities in the development of depressive symptoms and white matter alterations across species is thereby revealed. Data indicating that stress can interfere with physiological myelination patterns is presented. Altered myelination is most notably present in regions that are subject to maturation during the developmental stage of exposure to adversities.ConclusionTranslational studies point to replicable alterations in white matter integrity in subjects suffering from depression across multiple species. Impaired white matter integrity is apparent in imaging as well as neuropathological studies. Future studies should focus on determining to what extent influencing white matter integrity is able to improve symptoms of depression in animals as well as humans.
Business, biodiversity and ecosystem services: Evidence from large‐scale survey data
Authors: Wagner Marcus 
Published: June 2022

AbstractThis paper analyses data from a large‐scale survey on corporate action to support biodiversity and ecosystem services undertaken by firms of all sizes and across manufacturing industries. The analysis focuses on Germany as the largest economy by GDP in the European Union and analyses the uptake of activities directly aimed at protecting biodiversity and ecosystem services compared to the uptake of other environmental protection activities. It furthermore investigates how activity and tool adoption as well as risk assessments vary with firm size and across industries, and with implementing environmental management systems. The analysis finds tensions between risk perception and activities pursued for biodiversity protection, largely because firms shy away from substantive action. It reveals that smaller and medium‐sized firms are less active and that environmental management systems are not conducive to corporate activities in support of biodiversity and ecosystem services.
Incidence and time course of atrial fibrillation following patent foramen ovale closure
Authors: Krishnamurthy Yamini , Ben‐Ami Johanna , Robbins Barbara T. , Sommer Robert J. 
Published: June 2022

AbstractObjectivesDetermine the true incidence and time course of atrial fibrillation (AF) after patent foramen ovale closure (PFOc) using implantable loop recorders (ILR) placed during cryptogenic stroke evaluation.BackgroundPublished trials report a 2%–6.6% incidence of postimplant atrial fibrillation (PIAF) after PFOc, which is probably a gross underestimation, as only patients presenting in AF were captured. Episodes of paroxysmal and silent AF would have been missed.MethodsOf 761 patients who underwent PFOc at a single center between January 2016 and December 2020, 35 patients had an ILR implanted before PFOc, without documentation of AF, and had ≥1 month of monitoring post‐PFOc. The incidence, onset, and conclusion of AF episodes were determined from a review of patient records.ResultsThe mean duration of ILR monitoring was 54.6 ± 39.4 weeks after PFOc. AF occurred in 13/35 (37%) patients. PFOc patients who developed PIAF were older than those who did not (62 ± 11 vs. 52 ± 14 years, p = 0.03). In 12/13, the initial PIAF event occurred within 4 weeks of PFOc, with the greatest frequency around 2 weeks and conclusion by 12 weeks in all. No recurrent strokes occurred during ILR monitoring.ConclusionThe actual incidence of PIAF was far greater than previously reported and was significantly associated with older age at PFOc. The timing of PIAF onset and termination were consistent with a postimplant inflammatory mechanism. The higher actual PIAF incidence underscores its low stroke potential in this population. A larger prospective trial is required to validate these preliminary results.
Cu‐ and Fe‐Incorporated Manganese Oxides (MnxOy) as Cathodic Catalysts for Hydrogen Peroxide Reduction (HPR) and Oxygen Reduction (OR) in Micro‐direct Methanol Fuel Cells
Authors: Phuakkhaw Duangkamon , Amonpattaratkit Penphitcha , Klysubun Wantana , Saiwattanasuk Patraporn , Midpanon Supatta , Porntheeraphat Supanit , Klamchuen Annop , Wongchaisuwat Atchana , Sagawa Takashi , Viravathana Pinsuda 
Published: June 2022

AbstractImproving manganese oxides as cathodic catalysts in direct methanol/hydrogen peroxide fuel cells by incorporation of Cu and Fe to promote oxygen reduction (OR) and hydrogen peroxide reduction (HPR) is reported. The Cu‐incorporated and Fe‐incorporated MnxOy were prepared by impregnation and solvothermal processes. From XRD, XPS, and XAS analyses, the obtained MnxOy consisted of MnO2 and mixed phases of Mn3O4 and Mn2O3 from impregnation and solvothermal methods, respectively. The Cu‐incorporated and Fe‐incorporated MnxOy included CuO and Fe2O3, respectively, through both methods. Addition of Cu and Fe decreased the BET surface area and increased the pore sizes as compared to the pristine MnO2. With the Fe : Mn molar ratio of 0.20 : 1, the Fe‐incorporated MnxOy from the solvothermal method presented the highest cathodic peaks under the cyclic voltammogram of HPR and OR at around 0.59 V of 11.59 mA cm−2 and −0.59 V of −12.33 mA cm−2, respectively. Compared to the Cu‐incorporated ones, the highest HPR peak at 0.68 V of 9.20 mA cm−2 and the highest OR peak at −0.59 V of −6.99 mA cm−2 were obtained from the Cu‐incorporated MnxOy prepared through the solvothermal method at the Cu : Mn molar ratio of 0.15 : 1. Incorporating Cu or Fe into MnO2 brought the improvement of electrocatalytic activity for HPR and OR. The Cu‐incorporated and Fe‐incorporated MnxOy from both methods showed a higher power density of μ‐DMFC than the pristine MnO2.
Unfolding the structural features of NASICON materials for sodium‐ion full cells
Authors: Ahsan Muhammad Tayyab , Ali Zeeshan , Usman Muhammad , Hou Yanglong 
Published: June 2022

AbstractSodium‐ion batteries (SIBs) are potential candidates for the replacement of lithium‐ion batteries to meet the increasing demands of electrical storage systems due to the low cost and high abundance of sodium. Sodium superionic conductor (NASICON) structured materials have attracted enormous interest in recent years as electrode materials for safer and long‐term performance of SIBs for electric energy storage smart grids. These materials have a three‐dimensional robust framework, high redox potential, thermal stability, and a fast Na+‐ion diffusion mechanism. However, NASICON has low intrinsic electronic conductivity, which limits the electrochemical performance. This review describes the structural features of NASICONs to illustrate the ion storage mechanism and electrochemical performance of SIBs. Details of the NASICON crystal structure, the affiliated Na+‐ion diffusion mechanism, morphology, and electrochemical performance of these materials in sodium‐ion half‐cells as well as full cells are described. In addition to the application as electrode materials, the use of NASICONs as solid electrolytes is also elaborated in solid‐state SIBs. Based on these aspects, we have provided more perspectives in terms of the commercialization of SIBs and strategies to overcome the limitations of NASICONs. Hence, this review is expected to provide the researchers of energy storage with an in‐depth understanding of NASICON materials with the knowledge of structural features, which will provide a new avenue on the practicality of SIBs.
New Approaches toward Building Csp−P bond: A Two‐Decade Overview
Authors: Mele Lucas , Luc Pirat Jean , Ayad Tahar , Virieux David 
Published: June 2022

AbstractSince the review of Savignac, the past 20 years have seen significant progresses on the synthesis of alkynylphosphorus compounds considerably expanding the original and rather limited organic toolbox. This comprehensive review explores the latest and potentially greener methodologies using sustainable catalysis or direct metal‐free couplings from stable and easy to handle precursors. Recent progress and mechanistic insights for metal‐catalyzed reactions with a particular emphasis on copper, palladium, nickel and silver catalytic systems, photocatalytic and metal‐free reactions are detailed covering most of the publications related to this field since 2000 until March 2022.
Effect of Annulation Mode of Twistarene on the Physical Property and Self‐Assembly Behavior of Functionalized Curved Aromatic Molecules
Authors: Wang Wei , Yuan Ziwei , Wang Sujuan , Li Xueqing , Ji Bingliang , Xiao Jinchong 
Published: June 2022

AbstractFour novel curved polycyclic aromatic hydrocarbons 3 a, 5, 8, 15 a have been synthesized and characterized, where molecules 3 a and 15 a bear [5]carbohelicene units. X‐ray single crystal analyses indicate that compound 3 a shows offset packing arrangements of (P5)‐ and (M5)‐isomers, and 15 a has a symmetrical plane and looks like a butterfly. In comparison, 8 exhibits a slightly curved structure, in which the significant convex‐to‐convex π‐overlap with the shortest distance of 3.42 Å occurs. In addition, the effect of annulation mode of twistarenes on the physical properties, self‐assembly behaviors, and switchable photoconductivity of the as‐prepared curved aromatic compounds were further examined in a comparative manner.
Ag Doped Au44 Nanoclusters for Electrocatalytic Conversion of CO2 to CO
Authors: Tang Shisi , Xu Jiayu , Liu Xu , Zhu Yan 
Published: June 2022

AbstractA novel Ag doped Au44(C10H9)28 nanocluster (C10H10=1‐ethynyl‐2,4‐dimethylbenzene) was synthesized, that is, Ag4+xAu40‐x(C10H9)28 (x≤6), where four Ag positions located in the surface staple of the cluster have been determined, while six Au/Ag co‐occupying positions have been found in the metal core of the cluster. The electronic configuration of Au44(C10H9)28 cluster is significantly disturbed by doping Ag atoms, hence promoting the electron transport capability. For the two‐electron conversion reaction of CO2 to CO in electrochemical reduction of CO2, Ag doped Ag4+xAu40‐x(C10H9)28 catalyst exhibited higher effective activity and long‐term stability than its counterpart Au44(C10H9)28 catalyst.
Anomeric DNA Strand Displacement with α‐D Oligonucleotides as Invaders and Ethidium Bromide as Fluorescence Sensor for Duplexes with α/β‐, β/β‐ and α/α‐D Configuration
Authors: Zhang Aigui , Kondhare Dasharath , Leonard Peter , Seela Frank 
Published: June 2022

AbstractDNA strand displacement is a technique to exchange one strand of a double stranded DNA by another strand (invader). It is an isothermal, enzyme free method driven by single stranded overhangs (toeholds) and is employed in DNA amplification, mismatch detection and nanotechnology. We discovered that anomeric (α/β) DNA can be used for heterochiral strand displacement. Homochiral DNA in β‐D configuration was transformed to heterochiral DNA in α‐D/β‐D configuration and further to homochiral DNA with both strands in α‐D configuration. Single stranded α‐D DNA acts as invader. Herein, new anomeric displacement systems with and without toeholds were designed. Due to their resistance against enzymatic degradation, the systems are applicable to living cells. The light‐up intercalator ethidium bromide is used as fluorescence sensor to follow the progress of displacement. Anomeric DNA displacement shows benefits over canonical DNA in view of toehold free displacement and simple detection by ethidium bromide.
Electrocatalytic Hydrogen Evolution Using A Molecular Antimony Complex under Aqueous Conditions: An Experimental and Computational Study on Main‐Group Element Catalysis
Authors: Williams Caroline K. , McCarver Gavin A. , Chaturvedi Ashwin , Sinha Soumalya , Ang Marcus , Vogiatzis Konstantinos D. , Jiang Jianbing “Jimmy” 
Published: June 2022

AbstractElectrocatalytic hydrogen gas production is considered a potential pathway towards carbon‐neutral energy sources. However, the development of this technology is hindered by the lack of efficient, cost‐effective, and environmentally benign catalysts. In this study, a main‐group‐element‐based electrocatalyst, SbSalen, is reported to catalyze the hydrogen evolution reaction (HER) in an aqueous medium. The heterogenized molecular system achieved a Faradaic efficiency of 100 % at −1.4 V vs. NHE with a maximum current density of −30.7 mA/cm2. X‐ray photoelectron spectroscopy of the catalyst‐bound working electrode before and after electrolysis confirmed the molecular stability during catalysis. The turnover frequency was calculated as 43.4 s−1 using redox‐peak integration. The kinetic and mechanistic aspects of the electrocatalytic reaction were further examined by computational methods. This study provides mechanistic insights into main‐group‐element electrocatalysts for heterogeneous small‐molecule conversion.
An Anionic Amido‐Substituted Seven‐Vertex Siliconoid Cluster
Authors: Keuter Jan , Dimitrova Maria , Janka Oliver , Hepp Alexander , Berger Raphael J. F. , Lips Felicitas 
Published: June 2022

AbstractThe silanide [Si4{N(SiMe3)Dipp}3]−(1) transforms into the anionic siliconoid cluster [Si7{N(SiMe3)Dipp}3]−(2) with four unsubstituted silicon atoms as a contact ion pair with [K([18]crown‐6)] in C6D6at room temperature within five weeks. Anion2was investigated by natural population analysis and visualization of intrinsic atomic orbitals. Magnetically induced current‐density calculations of2revealed two distinct strong diatropic vortices that sum up in one direction and create a strongly shielded apical silicon atom in2.