bluuebunny/crossref_metadata_2025 huggingface dataset:
Uniform Chiral Near‐Fields in Achiral Nanocavity Induced by Magnetic Polaritons Mode
Authors: Bai Yu , Abudukelimu Abuduwaili , Zhang Ziyan , Ullah Hamad , Li Ying , Wang Yongkai , Zhang Zhongyue
Published: December 2021

Chiral near‐fields are crucial in the analysis of chiral molecules, circularly polarized luminescence, and sensing. Under circularly polarized light illumination, left‐ and right‐handed chiral near‐fields occur around nanostructures. However, most previously reported works require structural chirality based on asymmetric 3D nanostructures. Usually, left‐ and right‐handed chiral near‐fields are difficult to separate in space, leading to low efficiency in applications. Here, achiral U‐shaped groove nanostructure arrays are proposed to generate uniform chiral near‐fields under circularly polarized light illumination. In contrast to vertical parallel plate nanostructures, a bottom layer is added below the two vertical parallel plates to design U‐shaped groove nanostructures that induce magnetic polaritons mode. In the cavity of the achiral U‐shaped groove nanostructure, chiral near‐field is induced by the excitation of electric and magnetic near‐fields with parallel components. These chiral near‐fields strongly depend on the structural parameters of the U‐shaped groove nanostructure. In addition, chiral molecules are introduced into the cavity of the U‐shaped groove nanostructure to utilize it as sensors for chiral molecular detection. Numerical results show that the circular dichroism of the molecules is enhanced remarkably. These findings pave the way toward the development of practical and scalable platforms for new chiroptical applications.
Two‐Dimensional Polycyclic Photovoltaic Molecule with Low Trap Density for High‐Performance Photocatalytic Hydrogen Evolution
Authors: Zhang Zhenzhen , Si Wenqin , Wu Baohua , Wang Wei , Li Yawen , Ma Wei , Lin Yuze
Published: December 2021

Typical organic semiconductors show a high trap density of states (1016–1018 cm−3), providing a large number of centers for charge‐carrier recombination, thus hindering the development of photocatalytic hydrogen evolution. Here, we design and synthesize a two‐dimensional polycyclic photovoltaic material, named as TPP, to reduce the trap density to as low as 2.3×1015 cm−3, which is 1–3 orders of magnitude lower than those of typical organic semiconductors. Moreover, TPP exhibits a broad and strong absorption, ordered molecular packing with a large crystalline coherence length and enhanced electron mobility. Then, the bulk heterojunction nanoparticles (BHJ‐NPs) based on a blend of polymer donor (PM6) and TPP exhibit an average hydrogen evolution rate (HER) of 64.31 mmol h−1 g−1under AM1.5G sunlight (100 mW cm−2), and 72.75 mmol h−1 g−1under 330–1100 nm illumination (198 mW cm−2) higher than that of the control NPs based on typical PM6 : Y6 (62.67 mmol h−1 g−1).
Alkyl‐GeMe3: Neutral Metalloid Radical Precursors upon Visible‐Light Photocatalysis
Authors: Xu Qing‐Hao , Wei Li‐Pu , Xiao Bin
Published: December 2021

Single‐electron transfer (SET) oxidation of ionic hypervalent complexes, in particular alkyltrifluoroborates (Alkyl‐BF3−) and alkylbis(catecholato)silicates (Alkyl‐Si(cat)2−), have contributed substantially to alkyl radical generation compared to alkali or alkaline earth organometallics because of their excellent activity–stability balance. Herein, another proposal is reported by using neutral metalloid compounds, Alkyl‐GeMe3, as radical precursors. Alkyl‐GeMe3 shows comparable activity to that of Alkyl‐BF3− and Alkyl‐Si(cat)2− in radical addition reactions. Moreover, Alkyl‐GeMe3 is the first successful group 14 tetraalkyl nucleophile in nickel‐catalyzed cross‐coupling. Meanwhile, the neutral nature of these organogermanes offset the limitation of ionic precursors in purification and derivatization. A preliminary mechanism study suggests that an alkyl radical is generated from a tetraalkylgermane radical cation with the assistance of a nucleophile, which may also result in the development of more non‐ionic alkyl radical precursors with a metalloid center.
Saccharide‐Functionalized Poly(Zn‐salphen)‐alt‐(m‐ and p‐phenyleneethynylene)s as Dynamic Helical Metallopolymers
Authors: Zhao Chao , Meng Shuangshuang , Chan Hei‐Nga , Wang Xueli , Li Hung‐Wing , Chan Michael C. W.
Published: December 2021

The study of metallopolymers with controllable helical sense remains in its infancy. We report arabinose‐functionalized (Zn‐salphen)‐based conjugated polymers that display mirror‐image circular dichroism spectra for L‐ and D‐sugar sidechains respectively, signifying ordered (helical) coiling of the polymer backbone with opposite screw‐sense preferences. The observation of different spectroscopic behavior and Cotton effects for a variety of solvents (in a reversible manner) and temperatures, ascribed to changes in the extent of intrachain (Zn⋅⋅⋅O(salphen) and π‐stacking) interactions between Zn‐salphen moieties, thus indicate the flexible, responsive and dynamic nature of the folded helical conformation in these systems. An application study signifying that activity can be governed by the structure and helical sense of the polymer is described.
Tandem Living Insertion and Controlled Radical Polymerization for Polyolefin–Polyvinyl Block Copolymers
Authors: Keyes Anthony , Dau Huong , Matyjaszewski Krzysztof , Harth Eva
Published: December 2021

Practical synthesis of polyolefin–polyvinyl block copolymers remains a challenge for transition‐metal catalyzed polymerizations. Common approaches functionalize polyolefins for post‐radical polymerization via insertion methods, yet sacrifice the livingness of the olefin polymerization. This work identifies an orthogonal radical/spin coupling technique which affords tandem living insertion and controlled radical polymerization. The broad tolerance of this coupling technique has been demonstrated for diverse radical/spin traps such as 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐nitroxide (TIPNO), 1‐oxyl‐(2,2,6,6‐tetramethylpiperidine) ‐4‐yl‐α‐bromoisobutyrate (TEMPO‐Br), and N‐tert‐butyl‐α‐phenylnitrone (PBN). Subsequent controlled radical polymerization is demonstrated with nitroxide‐mediated polymerization (NMP) and atom transfer radical polymerization (ATRP), yielding polyolefin–polyvinyl di‐ and triblock copolymers (Đ<1.3) with acrylic, vinylic and styrenic segments. These findings highlight radical trapping as an approach to expand the scope of polyolefin‐functionalization techniques to access polyolefin macroinitiators.
Study on the structural evolution of polyacrylonitrile fibers in stepwise heat treatment process and its relationship with properties
Authors: Liu Yong , Liu Yu , Shang Lei , Ao Yuhui
Published: December 2021

The structural evolution of polyacrylonitrile fibers in stepwise heat treatment process and its relationship with properties were investigated systematically. Results demonstrated that the cyclization degree and dehydrogenation index of fibers reached 84.13% and 1.361, respectively after stabilization at 265°C. The oxygen reaction was enhanced after stabilized at 245°C. Refinement of the microcrystalline structure took effect during stabilization and low temperature carbonization, while growth of microcrystalline dominated during high temperature carbonization. The results of surface topography study not only provided the evolution characteristics of surface microstructure under the influence of chemical reaction, but also further complements the internal aggregation structural rearrangement process from the side. Additionally, the temperature zone from 245 to 265°C was the key stage of the formation of the skin‐core structure, which would be transmitted to the resultant carbon fiber. Tensile strength and tensile modulus decreased during stabilization stage, reaching 4.273 GPa and 221.132 GPa, respectively after high temperature carbonization. The elongation at break which first increased and then decreased proved a toughness failure to brittleness failure. The investigation elucidated the relationship between the mechanical property with chemical and physical microstructure. And the possible rearrangement process of the aggregation structure was proposed.
The relationship between autism spectrum and sleep–wake traits
Authors: Elkhatib Smidt Stacey D. , Ghorai Arpita , Taylor Sara C. , Gehringer Brielle N. , Dow Holly C. , Langer Allison , Rawot Eric , Zhang Jing , Mitchell Jonathan A. , Rader Daniel J. , Almasy Laura , Brodkin Edward S. , Bućan Maja
Published: December 2021

Autistic children and adults often have sleep disturbances, which may affect their and their family's quality of life. Yet, the relationship between sleep–wake patterns and autism spectrum traits is understudied. Identifying such relationships could lead to future research elucidating common mechanistic underpinnings. Thus, we aimed to determine whether sleep–wake patterns, specifically related to sleep, physical activity, and the daily sleep–wake rhythm (i.e., circadian rhythm), are associated with autism spectrum‐related traits. Accelerometer‐derived sleep–wake parameters were estimated in individuals with autistic spectrum traits and their family members (N = 267). We evaluated autism spectrum traits using the Social Responsiveness Scale (SRS) to assess the presence and severity of social impairment and the Behavior Rating Inventory of Executive Function (BRIEF) to assess executive function. The linear multivariate regression analysis (using SOLAR‐Eclipse) showed that in adults, increased core autism spectrum traits and executive dysfunction were associated with disruption of several sleep–wake parameters, particularly related to the daily sleep–wake rhythm, and that executive dysfunction was associated with disrupted sleep quality and level of physical activity. We highlight the interplay between daytime function and disrupted sleep–wake patterns, specifically related to the daily sleep–wake rhythm, that could guide future research into common mechanisms.

Lay Summary

Autistic children and adults often report sleep disturbances. To dissect the relationship between a range of autism spectrum traits and sleep–wake patterns, we assessed social interaction and executive function in participants who also wore actimetry watches on their wrists to assess their sleep–wake patterns. We found that increased impairments in social and executive function occurred with increased sleep–wake disturbances, particularly those related to the circadian rhythm, suggesting that these perturbations/disruptions in the sleep–wake cycle could be connected to autism spectrum traits.
Rare variants in the outcome of social skills group training for autism
Authors: Li Danyang , Choque Olsson Nora , Becker Martin , Arora Abishek , Jiao Hong , Norgren Nina , Jonsson Ulf , Bölte Sven , Tammimies Kristiina
Published: December 2021

Exome sequencing has been proposed as the first‐tier genetic testing in autism spectrum disorder (ASD). Here, we performed exome sequencing in autistic individuals with average to high intellectual abilities (N = 207) to identify molecular diagnoses and genetic modifiers of intervention outcomes of social skills group training (SSGT) or standard care. We prioritized variants of clinical significance (VCS), variants of uncertain significance (VUS) and generated a pilot scheme to calculate genetic scores of rare and common variants in ASD‐related gene pathways. Mixed linear models were used to test the association between the carrier status of VCS/VUS or the genetic scores with intervention outcomes measured by the social responsiveness scale. Additionally, we combined behavioral and genetic features using a machine learning (ML) model to predict the individual response. We showed a rate of 4.4% and 11.3% of VCS and VUS in the cohort, respectively. Individuals with VCS or VUS had improved significantly less after standard care than non‐carriers at post‐intervention (β = 9.35; p = 0.036), while no such association was observed for SSGT (β = −2.50; p = 0.65). Higher rare variant genetic scores for synaptic transmission and regulation of transcription from RNA polymerase II were separately associated with less beneficial (β = 8.30, p = 0.0044) or more beneficial (β = −6.79, p = 0.014) effects after SSGT compared with standard care at follow‐up, respectively. Our ML model showed the importance of rare variants for outcome prediction. Further studies are needed to understand genetic predisposition to intervention outcomes in ASD.
The flagellar germ‐line hypothesis: How flagellate and ciliate gametes significantly shaped the evolution of organismal complexity
Authors: Lindemann Charles B.
Published: December 2021

This essay presents a hypothesis which contends that the development of organismic complexity in the eukaryotes depended extensively on propagation via flagellated and ciliated gametes. Organisms utilizing flagellate and ciliate gametes to propagate their germ line have contributed most of the organismic complexity found in the higher animals. The genes of the flagellum and the flagellar assembly system (intraflagellar transport) have played a disproportionately important role in the construction of complex tissues and organs. The hypothesis also proposes that competition between large numbers of haploid flagellated male gametes rigorously conserved the functionality of a key set of flagellar genes for more than 700 million years. This in turn has insured that a large set (>600) of highly functional cytoskeletal and signal pathway genes is always present in the lineage of organisms with flagellated or ciliated gametes to act as a dependable resource, or “toolkit,” for organ elaboration. Also see the video abstract here: https://youtu.be/lC5nC-WOcm8
Altered brain activity in end‐stage knee osteoarthritis revealed by resting‐state functional magnetic resonance imaging
Authors: Kang Bing‐Xin , Ma Jie , Shen Jun , Xu Hui , Wang Hai‐Qi , Zhao Chi , Xie Jun , Zhong Sheng , Gao Chen‐Xin , Xu Xi‐Rui , A Xin‐Yu , Gu Xiao‐Li , Xiao Lianbo , Xu Jianguang
Published: December 2021

Introduction

Knee osteoarthritis (KOA) is characterized by a degenerative change of knee cartilage and secondary bone hyperplasia, resulting in pain, stiffness, and abnormal walking gait. Long‐term chronic pain causes considerable cortical plasticity alternations in patients. However, the brain structural and functional alterations associated with the pathological changes in knee joints of end‐stage KOA patients remain unclear. This study aimed to analyze the structural and functional connectivity alterations in end‐stage KOA to comprehensively understand the main brain‐associated mechanisms underlying its development and progression.

Methods

In this study, 37 patients with KOA and 37 demographically matched healthy controls (HCs) were enrolled. Alternations in gray matter (GM) volume in patients with KOA were determined using voxel‐based morphometry. The region with the largest GM volume alteration was selected as the region of interest to calculate the voxel‐wise resting‐state functional connectivity (rs‐FC) in the two groups. Pearson's correlation coefficient was used to analyze the correlation between clinical measures and GM volume alternations in patients with KOA.

Results

Compared with HCs, patients with KOAs exhibited significantly decreased GM volumes in the left middle temporal gyrus (left‐MTG) and the left inferior temporal gyrus. Results of the voxel‐wise rs‐FC analysis revealed that compared with HCs, patients with KOA had decreased left‐MTG rs‐FC to the right dorsolateral superior frontal gyrus, left middle frontal gyrus, and left medial superior frontal gyrus. GM volume in the left‐MTG was negatively correlated with the Western Ontario and McMaster Universities Arthritis Index in patients with KOA (r = −0.393, p = .016).

Conclusion

Structural remodeling and functional connectivity alterations may be one of the central brain mechanisms associated with end‐stage KOA.
Development, application, and evaluation of an online competitive simulation game for teaching electricity markets
Authors: Giraldo Juan S. , Kok Koen , Paterakis Nikolaos G.
Published: December 2021

The decline of fresh‐enrolled students and the increase in the number of dropouts in electrical engineering schools might be related to motivation, engagement and differences in learning preferences. This paper provides a detailed description of the development, application, and evaluation of an online, asynchronous simulation game to teach electricity markets concepts named EMGA. The EMGA aims to introduce students to the short‐term electricity market structure, highlighting the importance of forecasting tools for decision‐making. The EMGA has been deployed in a Master's course with 27 students. The learning effectiveness was assessed with a survey at the end of the exercise. Questions aiming at experience generation, conceptual understanding, skills development and affective evaluation were enquired. Positive results towards experience generation, conceptual understanding and affective evaluation were obtained. Students felt optimistic about the platform's potential. The main complaints from students were their lack of programming experience and the allocated time for the exercise during the course. Results from this small test, along with previously obtained results, are encouraging and might be of potential use for further developing the EMGA and student's experience.
Bioresorbable magnesium scaffold in the treatment of simple coronary bifurcation lesions: The BIFSORB pilot II study
Authors: Barkholt Trine Ø. , Neghabat Omeed , Holck Emil N. , Andreasen Lene N. , Christiansen Evald H. , Holm Niels R.
Published: December 2021

Objectives

To evaluate the feasibility, safety, and healing response of a magnesium‐based bioresorbable scaffold (BRS) in the treatment of simple bifurcation lesions using the single stent provisional technique.

Background

BRS may hold potential advantages in the treatment of coronary bifurcation lesions, however low radial strength and expansion capacity has been an issue with polymer‐based scaffolds. The magnesium BRS may prove suitable for bifurcation treatment as its mechanical properties are closer to those of permanent metallic drug‐eluting stents.

Methods

The study was a proof‐of‐concept study with planned inclusion of 20 patients with stable angina pectoris and a bifurcation lesion involving a large side branch (SB) > 2.5 mm with less than 50% diameter stenosis. Procedure and healing response were evaluated by optical coherence tomography (OCT). The main endpoints were a composite clinical safety endpoint and an OCT healing index at 1 month (range: 0–98).

Results

Eleven patients were included in the study. The study was prematurely terminated due to scaffold fractures and embolization of scaffold fragments in three cases requiring bailout stenting with drug‐eluting stents. One patient underwent bypass surgery at 3 months due to stenosis proximal to the study segment. All SB were patent for 1 month. One‐month OCT evaluation showed strut coverage of 96.9% and no malapposition. Scaffold fractures and uncovered jailing struts resulted in a less favorable mean OCT healing index score of 10.4 ± 9.0.

Conclusions

Implanting a magnesium scaffold by the provisional technique in nontrue bifurcation lesions was associated with scaffold fracture, embolization of scaffold fragments, and a high need for bailout stenting.
Impact of COVID‐19 pandemic on the management of nonculprit lesions in patients presenting with ST‐elevation myocardial infarction: Outcomes from the pan‐London heart attack centers
Authors: Demir Ozan M. , Little Callum D. , Jabbour Richard , Rahman Haseeb , Sayers Max , Ahmed Asrar , Connolly Michelle J. , Kanyal Ritesh , MacCarthy Philip , Wilson Simon J. , Dalby Miles , Jain Ajay , Malik Iqbal , Rakhit Roby , Perera Divaka
Published: December 2021

Background

The impact of COVID‐19 on the diagnosis and management of nonculprit lesions remains unclear.

Objectives

This study sought to evaluate the management and outcomes of patients with nonculprit lesions during the COVID‐19 pandemic.

Methods

We conducted a retrospective observational analysis of consecutive primary percutaneous coronary intervention (PPCI) pathway activations across the heart attack center network in London, UK. Data from the study period in 2020 were compared with prepandemic data in 2019. The primary outcome was the rate of nonculprit lesion percutaneous coronary intervention (PCI) and secondary outcomes included major adverse cardiovascular events.

Results

A total of 788 patients undergoing PPCI were identified, 209 (60%) in 2020 cohort and 263 (60%) in 2019 cohort had nonculprit lesions (p = .89). There was less functional assessment of the significance of nonculprit lesions in the 2020 cohort compared to 2019 cohort; in 8% 2020 cohort versus 15% 2019 cohort (p = .01). There was no difference in rates of PCI for nonculprit disease in the 2019 and 2020 cohorts (31% vs 30%, p = .11). Patients in 2020 cohort underwent nonculprit lesion PCI sooner than the 2019 cohort (p < .001). At 6 months there was higher rates of unplanned revascularization (4% vs. 2%, p = .05) and repeat myocardial infarction (4% vs. 1%, p = .02) in the 2019 cohort compared to 2020 cohort.

Conclusion

Changes to clinical practice during the COVID‐19 pandemic were associated with reduced rates of unplanned revascularization and myocardial infarction at 6‐months follow‐up, and despite the pandemic, there was no difference in mortality, suggesting that it is not only safe but maybe more efficacious.
Pertraction of Vanadium(V) from Dilute Acidic Media by an Emulsion Liquid Membrane Containing a Commercial Extractant
Authors: Nabavinia Mahbooneh , Kargari Ali , Soleimani Mansooreh
Published: December 2021

Emulsion liquid membrane (ELM) pertraction of VV ions from dilute acidic solution by using a mixture of di(2‐ethylhexyl)phosphoric acid (D2EHPA) and mono(2‐ethylhexyl)phosphoric acid (M2EHPA) was studied. First, solvent extraction of VV from an aqueous medium was performed, and the optimum feed pH and extractant concentration were obtained. Tributyl phosphate was used as modifier to increase membrane stability and decrease membrane swelling. The effects of diluent type, extractant concentration of the emulsifier concentration, stripping reagent concentration (sulfuric acid), organic phase/stripping phase volume ratio, emulsification time and speed, feed initial pH, agitation speed, temperature, and contact time on VV extraction efficiency and ELM stability were considered.
Rh‐Catalyzed Coupling of Aldehydes with Allylboronates Enables Facile Access to Ketones
Authors: Zhang Kezhuo , Huang Jiaxin , Zhao Wanxiang
Published: December 2021

We present herein a novel strategy for the preparation of ketones from aldehydes and allylic boronic esters. This reaction involves the allylation of aldehydes with allylic boronic esters and the Rh‐catalyzed chain‐walking of homoallylic alcohols. The key to this successful development is the protodeboronation of alkenyl borylether intermediate via a tetravalent borate anion species in the presence of KHF2 and MeOH. This approach features mild reaction conditions, broad substrate scope, and excellent functional group tolerance. Mechanistic studies also supported that the tandem allylation and chain‐walking process were involved.
Electrostatic Perturbations in the Substrate‐Binding Pocket of Taurine/α‐Ketoglutarate Dioxygenase Determine its Selectivity
Authors: Ali Hafiz Saqib , de Visser Sam P.
Published: December 2021

Taurine/α‐ketoglutarate dioxygenase is an important enzyme that takes part in the cysteine catabolism process in the human body and selectively hydroxylates taurine at the C1‐position. Recent computational studies showed that in the gas‐phase the C2−H bond of taurine is substantially weaker than the C1−H bond, yet no evidence exists of 2‐hydroxytaurine products. To this end, a detailed computational study on the selectivity patterns in TauD was performed. The calculations show that the second‐coordination sphere and the protonation states of residues play a major role in guiding the enzyme to the right selectivity. Specifically, a single proton on an active site histidine residue can change the regioselectivity of the reaction through its electrostatic perturbations in the active site and effectively changes the C1−H and C2−H bond strengths of taurine. This is further emphasized by many polar and hydrogen bonding interactions of the protein cage in TauD with the substrate and the oxidant that weaken the pro‐R C1−H bond and triggers a chemoselective reaction process. The large cluster models reproduce the experimental free energy of activation excellently.
Li5SnP3 – a Member of the Series Li10+4xSn2−xP6 for x=0 Comprising the Fast Lithium‐Ion Conductors Li8SnP4 (x=0.5) and Li14SnP6 (x=1)
Authors: Strangmüller Stefan , Müller David , Raudaschl‐Sieber Gabriele , Kirchhain Holger , van Wüllen Leo , Fässler Thomas F.
Published: December 2021

The targeted search for suitable solid‐state ionic conductors requires a certain understanding of the conduction mechanism and the correlation of the structures and the resulting properties of the material. Thus, the investigation of various ionic conductors with respect to their structural composition is crucial for the design of next‐generation materials as demanded. We report here on Li5SnP3 which completes with x=0 the series Li10+4xSn2−xP6 of the fast lithium‐ion conductors α‐ and β‐Li8SnP4 (x=0.5) and Li14SnP6 (x=1). Synthesis, crystal structure determination by single‐crystal and powder X‐ray diffraction methods, as well as 6Li, 31P and 119Sn MAS NMR and temperature‐dependent 7Li NMR spectroscopy together with electrochemical impedance studies are reported. The correlation between the ionic conductivity and the occupation of octahedral and tetrahedral sites in a close‐packed array of P atoms in the series of compounds is discussed. We conclude from this series that in order to receive fast ion conductors a partial occupation of the octahedral vacancies seems to be crucial.
Gene pyramiding combinations confer resistance of Asian soybean rust
Authors: Meira Daniela , Panho Maiara Cecilia , Beche Eduardo , Woyann Leomar Guilherme , Madella Laura Alexandra , Milioli Anderson Simionato , Colonelli Lucas Leite , Malone Gaspar , Brito Salvador Lima , Benin Giovani
Published: December 2021

Pyramiding Rpp genes is a promising strategy to achieve a more durable resistance against Asian soybean rust (ASR). The objective of this study was to develop Rpp‐pyramided populations and evaluate their resistance and yield in field conditions. Fifteen pyramided populations carrying different combinations of Rpp genes were developed, and the F3 lines were evaluated to phenotypic resistance and yield performance. Our results suggest that the Rpp1‐b of different resistant sources (PI 587880A, PI 594723, PI 4538A) have higher resistance and yield performance compared with other Rpp genes. Rpp‐pyramided populations carrying two and three genes showed an increase in resistance compared with populations carrying a single Rpp gene. The best gene combinations were Rpp1‐b + Rpp5, showing neither uredinia formation nor sporulation (immunity + RB1 phenotype reaction) in more than 70% of the F3 population. Rpp‐pyramided lines developed in this study have the potential to be used in backcross programs for improving ASR resistance.
Stochasticity of individual competition and local matchup inequality for saplings in a niche‐structured forest
Authors: Hoshizaki Kazuhiko , Takahashi Satoshi , Tanaka Hiroshi , Oki Shinji , Matsushita Michinari
Published: December 2021

Ecologists have recently accepted the notion that species coexistence involves both niche and neutral processes, but few studies have explained how both of these opposite views can explain coexistence in the same community. Here we focus on competition among sessile organisms and explored first the extent to which species‐based niche reflects local “matchups” between nearby individuals, using 726 saplings of 10 temperate tree species, and second the members engaging in the matchups, which have rarely been quantified despite the importance in mixed‐species forests. Growth responses to light showed considerable species‐level differences, suggesting commonly seen regeneration niches. Outcomes of the individual matchups were basically predictable from the species mean response, but also with substantial contribution of within‐species variation. We found strong imbalance in matchup frequencies, such that some individuals meet more individuals of differing species but others meet fewer, as well as many isolated, competition‐free ones. The niche and neutral processes appear to reflect, respectively, between‐ and within‐species differences, and our findings suggest that even when niche segregation is discernible, the role of stochasticity for the frequency of local competition, as well as its outcomes, cannot be discounted in species coexistence.
Do trade‐offs govern plant species’ responses to different global change treatments?
Authors: Langley J. Adam , Grman Emily , Wilcox Kevin R. , Avolio Meghan L. , Komatsu Kimberly J. , Collins Scott L. , Koerner Sally E. , Smith Melinda D. , Baldwin Andrew H. , Bowman William , Chiariello Nona , Eskelinen Anu , Harmens Harry , Hovenden Mark , Klanderud Kari , McCulley Rebecca L. , Onipchenko Vladimir G. , Robinson Clare H. , Suding Katharine N.
Published: December 2021

Plants are subject to trade‐offs among growth strategies such that adaptations for optimal growth in one condition can preclude optimal growth in another. Thus, we predicted that a plant species that responds positively to one global change treatment would be less likely than average to respond positively to another treatment, particularly for pairs of treatments that favor distinct traits. We examined plant species’ abundances in 39 global change experiments manipulating two or more of the following: CO2, nitrogen, phosphorus, water, temperature, or disturbance. Overall, the directional response of a species to one treatment was 13% more likely than expected to oppose its response to a another single‐factor treatment. This tendency was detectable across the global data set, but held little predictive power for individual treatment combinations or within individual experiments. Although trade‐offs in the ability to respond to different global change treatments exert discernible global effects, other forces obscure their influence in local communities.
Catecholamine‐induced cardiomyopathy improvement after para‐aortic paraganglioma resection: a case report
Authors: Ranjbar Maryam , Amin Ahmad , Totonchi Ziae , Ghaemmaghami Zahra , Jalilian Zahra , Hesami Mahshid , Givtaj Nader , Jadbabaei Amir Nasser , Divanbeigi Iman , Mazloomfard Mohammad Mohsen
Published: December 2021

Phaeochromocytomas/paragangliomas (PPGL) are rare tumours that can cause cardiovascular complications following the secretion of catecholamines. We present a young female presented with heart failure with reduced ejection fraction as a result of norepinephrine secreting para‐aortic paraganglioma and improvement of heart failure sign and symptoms and left ventricular ejection fraction following tumour resection.
Phosphorescent Complexes of {Mo6I8}4+ and {W6I8}4+ with Perfluorinated Aryl Thiolates featuring Unusual Molecular Structures
Authors: Mironova Alina D. , Mikhaylov Maksim A. , Maksimov Alexander M. , Brylev Konstantin A. , Gushchin Artem L. , Stass Dmitry V. , Novikov Alexander S. , Eltsov Ilia V. , Abramov Pavel A. , Sokolov Maxim N.
Published: December 2021

A series of six novel cluster complexes [M6I8(SArf)6]2− (M=Mo or W; SArf=p‐SC6F4‐C6F5, p‐SC6F4Cl, or p‐SC6F4CF3) was prepared by exchange reactions between [Mo6I14]2− or [W6I14]2− and silver salts of the corresponding thiols and characterized by X‐ray single‐crystal diffraction and elemental analysis, NMR, ESI‐MS, and CV techniques. In the crystal structures all the thiolate ligands adopt an idiosyncratic orientation along one of the idealized three‐fold axes passing through two opposite μ3‐I ligands and the centers of two opposite faces of the M6 octahedra. This leads to shortened intramolecular C⋅⋅⋅I distances inside the cluster below 3.5 Å. The clusters exhibit red photoluminescence with relatively high quantum yield, up to 0.42 in the case of (Bu4N)2[W6I8(SC6F4CF3)6]. Moreover, all the compounds exhibit X‐ray luminescence; the close values of the maxima in the photo‐ and X‐ray induced emission spectra indicate that the luminescence is cluster‐centered.
A [1H,15N] Heteronuclear Single Quantum Coherence NMR Study of the Solution Reactivity of the Ruthenium‐Based Mitochondrial Calcium Uniporter Inhibitor Ru265
Authors: Woods Joshua J. , Spivey Jesse A. , Wilson Justin J.
Published: December 2021

The synthesis and characterization of the 15N‐labeled analogue of the mitochondrial calcium uptake inhibitor [Cl(NH3)4Ru(μ‐N)Ru(NH3)4Cl]3+ (Ru265) bearing [15N]NH3 ligands is reported. Using [1H,15N] HSQC NMR spectroscopy, the rate constants for the axial chlorido ligand aquation of [15N]Ru265 in pH 7.4 buffer at 25 °C were found to be k1=(3.43±0.03)×10−4 s−1 and k2=(4.03±0.09)×10−3 s−1. The reactivity of [15N]Ru265 towards biologically relevant small molecules was also assessed via this method, revealing that this complex can form coordination bonds to anionic oxygen and sulfur donors. Time‐based studies on these ligand‐binding reactions reveal this process to be slow relative to the time required for the complex to inhibit mitochondrial calcium uptake, suggesting that hydrogen‐bonding interactions, rather than the formation of coordination bonds, may play a more significant role in mediating the inhibitory properties of this complex.
Multispin Systems with a Rigid Ferrocene‐1,1′‐diyl‐Substituted 1,3‐Diazetidine‐2,4‐diimine Coupler: A General Approach
Authors: Gurskaya Larisa Yu. , Polienko Yuliya F. , Rybalova Tatyana V. , Gritsan Nina P. , Dmitriev Alexey A. , Kazantsev Maxim S. , Zaytseva Elena V. , Parkhomenko Dmitry A. , Beregovaya Irina V. , Zakabluk Galina A. , Tretyakov Evgeny V.
Published: December 2021

This paper describes the stepwise aza‐Wittig reaction of 1,1′‐bis(triphenylphosphoranylidenamino)‐ferrocene with a paramagnetic isocyanate, namely, 3‐isocyanato‐2,2,5,5‐tetramethyl‐2,5‐dihydro‐1H‐pyrrole‐1‐oxyl, and then with substituted arylisocyanates. The intermediate product (a paramagnetic betaine), which is the product of an intramolecular nucleophilic attack of the nitrogen atom of the iminophosphorane moiety on the carbon atom of the carbodiimide functional group, was isolated and structurally characterized. Subsequent interaction of the betaine with arylisocyanates under mild conditions gave spin‐labeled ferrocenophanes with the 1,3‐diazetidine‐2,4‐diimine coupler. It was found that the mutual arrangement of the substituents in the latter depends on the nature of the substituents in the arylisocyanate. Iodophenyl derivatives of 1,3‐diazetidine‐2,4‐diimines were cross‐coupled with the gold(I) nitronyl nitroxide‐2‐ide complex, thus yielding diradicals: metallocenophanes functionalized with various types of nitroxide substituents. Molecular and crystal structures of all mono‐ and diradicals were solved by X‐ray diffraction analysis.
High Sensitive Voltammetric Gentamicin Sensor using Poly (3‐thiophenecarboxylic acid‐co‐3‐methylthiophene) Modified Glassy Carbon Electrode
Authors: Burç Muammer , Titretir Duran Serap , Güngör Öznur , Köytepe Süleyman
Published: December 2021

For the determination of gentamicin in biomedical applications, sensitive, fast and low cost voltammetric sensor has been developed. Prepared sensor was successfully used for determination of gentamicine in synthetic urine samples with different voltammetric measurement methods. Firstly, glassy carbon electrode was modified using cyclic voltammetry technique by electropolymerization of 3‐thiophenecarboxylic acid and 3‐methylthiophene. Then, optimization of the electrochemical parameters was carried out for modified electrode. With this modified electrode, gentamicin determination was performed in the linear range of 0.05–4.00 mM. The correlation coefficient, limit of detection and limit of quantitation were calculated as 0.9999, 0.039 mM and 0.129 mM, respectively.
Effect of Nickel Precursor on the Catalytic Performance of Graphene Aerogel‐Supported Nickel Nanoparticles for the Production of COx‐free Hydrogen by Ammonia Decomposition
Authors: Kocer Tolga , Saraç-Öztuna F. Eylül , Kurtoğlu-Öztulum Samira F. , Unal Ugur , Uzun Alper
Published: December 2021

Graphene aerogel (GA), a promising porous material with high specific surface area and electrical conductivity, is utilized to disperse nickel nanoparticles to reach high catalytic activity in COx‐free hydrogen production from ammonia. Ni(NO3)2·6H2O and Ni (II) acetylacetonate (Ni(acac)2) were considered as metal precursors and the pH of the impregnation solution was varied to investigate the effects on the catalytic properties of the GA‐supported nickel catalysts. Data showed that the best dispersion and homogeneity, as well as the catalytic performance, is achieved with Ni(acac)2. An average Ni nanoparticle size of 13.6 ± 4.3 nm was obtained on the GA‐supported catalyst prepared by using Ni(acac)2 dissolved in an impregnation solution with a pH of 10.2. This catalyst with a Ni loading of 11.1 wt% provided an ammonia conversion of 70.2% at a space velocity of 30 000 mL NH3 gcat−1 h−1 and 600 °C corresponding to a hydrogen production rate of 21.5 mmol H2 gcat−1 min−1. Data illustrated that the difference between the point of zero charge of the support and the pH of the impregnation solution set by the type of the Ni precursor is a major parameter controlling the metal dispersion and the consequent catalytic activity.
CN‐3 increases TMZ sensitivity and induces ROS‐dependent apoptosis and autophagy in TMZ‐resistance glioblastoma
Authors: Xue Yu‐Ye , Lu Yun‐Yang , Sun Guang‐Qiang , Fang Fei , Ji Yu‐Qiang , Tang Hai‐Feng , Qiu Peng‐Cheng , Cheng Guang
Published: December 2021

Many glioma patients develop resistance to temozolomide (TMZ) treatment, resulting in reduced efficacy and survival rates. TMZ‐resistant cell lines SHG44R and U87R, which highly express O6‐methylguanine DNA methyltransferase (MGMT) and P‐gp, were established. CN‐3, a new asterosaponin, showed cytotoxic effects on TMZ‐resistant cells in a dose‐ and time‐dependent manner via reactive oxygen species (ROS)‐mediated apoptosis and autophagy. Transmission electron microscopy and monodansylcadaverine (MDC) staining showed turgidity of the mitochondria and autophagosomes in CN‐3‐treated SHG44R and U87R cells. The autophagy inhibitor 3‐methyladenine was used to confirm the important role of autophagy in CN‐3 cytotoxicity in TMZ‐resistant cells. The ROS scavenger N‐acetyl‐
l‐cysteine (NAC) attenuated the levels of ROS induced by CN‐3 and, therefore, rescued the CN‐3 cytotoxic effect on the viability of SHG44R and U87R cells by Cell Counting Kit‐8 assays and JuLI‐Stage videos. MDC staining also confirmed that NAC rescued an autophagosome increase in CN‐3‐treated SHG44R and U87R cells. Western blotting revealed that CN‐3 increased Bax, cleaved‐caspase 3, cytochrome C, PARP‐1, LC3‐Ⅱ, and Beclin1, and decreased P‐AKT, Bcl‐2, and p62. Further rescue experiments revealed that CN‐3 induced apoptosis and autophagy through ROS‐mediated cytochrome C, cleaved‐caspase 3, Bcl‐2, P‐AKT, PARP‐1, and LC3‐Ⅱ. In addition, CN‐3 promoted SHG44R and U87R cells sensitive to TMZ by reducing the expression of P‐gp, MGMT, and nuclear factor kappa B p65, and it had a synergistic cytotoxic effect with TMZ. Moreover, CN‐3 disrupted the natural cycle arrest and inhibited the migration of SHG44R and U87R cells by promoting cyclin E1 and D1, and by decreasing P21, P27, N‐cadherin, β‐catenin, transforming growth factor beta 1, and Smad2.
Infectious risks in patients treated with extracorporeal photopheresis for graft‐versus‐host disease: A retrospective cohort study
Authors: Thevenet Ugo , Daguenet Elisabeth , Beszera Silvia‐Maria , Cornillon Jérôme , Tavernier Emmanuelle , Schein Flora , Honeyman Fressia , Guyotat Denis
Published: December 2021

Background

Infections are common with significant mortality and morbidity in patients with graft‐versus‐host disease (GvHD). Extracorporeal photopheresis (ECP) is an advantageous treatment option for patients with GvHD because it is not immunosuppressive. The objective of this study was to assess the rate of infections and to determine risk factors in patients with GvHD.

Materials and Methods

In a single‐center cohort, we retrospectively collected data on infectious episodes by evaluating the clinical records of patients with GvHD treated by ECP since 2011.

Results

A total of 47 patients were included in this study. At ECP initiation, there were 10 patients with acute GvHD and 37 with chronic GvHD. At the final follow‐up, 200 infectious episodes were diagnosed in 91.5% of patients with an average follow‐up of 25.9 months (ie, 1.97 infections per patient per year). Most episodes had positive outcomes as there was no death related to infections, and only six infections required long‐term treatment. Higher dose of corticosteroids at the initiation of ECP was significantly associated with a shorter onset of the first infection (hazard ratio [HR] = 2.05; 95% confidence interval [CI] [1.17, 3.57]; P = .013). Unrelated donor transplants were significantly associated with a lower rate of infection (HR = 0.61; 95% CI [0.39, 0.95]; P = .028).

Conclusion

The results of our study suggest that ECP is associated with a low infection rate and an optimal clinical efficacy. Thus, ECP is still a suitable treatment for GvHD. Yet, a future study with a larger cohort will be necessary to deepen the identification of risk factors for infection.
Factors associated with county‐level mental health during the COVID‐19 pandemic
Authors: Lupton‐Smith Carly , Badillo‐Goicochea Elena , Chang Ting‐Hsuan , Maniates Hannah , Riehm Kira E. , Schmid Ian , Stuart Elizabeth A.
Published: December 2021

The objective of this study is to determine county‐level factors associated with anxiety, depression, and isolation during the coronavirus disease 2019 (COVID‐19) pandemic. This study used daily data from 23,592,355 respondents of a nationwide Facebook‐based survey from April 2020 to July 2021, aggregated to the week‐county level to yield 212,581 observations. Mental distress prevalences were modeled using weighted linear mixed‐effects models with a county random effect. These models revealed that weekly percentages of mental distress were higher in counties with higher unemployment rates, populations, and education levels; higher percentages of females, young adults, individuals with a medical condition, and individuals very worried about their finances and COVID‐19; and lower percentages of individuals who were working outside the home, living with children, without health insurance, and Black. Anxiety peaked in April 2020, depression in October 2020, and isolation in December 2020. Therefore, United States counties experienced the mental health effects of the pandemic differently dependent upon their characteristics, and mental distress prevalence varied across time.
Efficacy and Safety of Adjunctive Serotonin‐Dopamine Activity Modulators in Major Depression: A Meta‐Analysis of Randomized Controlled Trials
Authors: Mishra Archana , Sarangi Sudhir Chandra , Maiti Rituparna , Sood Mamta , Reeta KH
Published: December 2021

Serotonin‐dopamine activity modulators (SDAMs) have been approved as an adjunctive treatment to antidepressants in patients with inadequate response. These drugs have been proposed to have a beneficial effect on cognition, sleep‐related problems, and other affective symptoms in patients with depression. Previous studies have shown inconsistent evidence and have not reported a pooled effect of the 2 drugs of this class: aripiprazole and brexpiprazole. This meta‐analysis evaluated the effect of augmentation with SDAM drugs in patients with major depression. The meta‐analysis protocol was made as per Preferred Reporting Items for Systematic Reviews and Meta‐Analysis Protocol guidelines and registered in the International Prospective Register of Ongoing Systematic Reviews. The PubMed/MEDLINE, Cochrane Clinical Trial registry, and EudraCT databases were searched with prespecified search terms. A random‐effects meta‐analysis was performed using the meta package in R software. Fifteen studies were included in this meta‐analysis. The random‐effects model analysis observed a pooled effect of 1.55 (95%CI, 1.32‐1.84; prediction interval, 0.95‐2.55, z = 5.19 [P < .0001]) for remission between the SDAM and placebo groups. A pooled effect of 1.58 (95%CI, 1.37‐1.83; prediction interval, 1.00–2.51, z = 6.34 [P < .0001]) for adverse events and 0.72 (95%CI, 0.48‐1.08; prediction interval, 0.46‐1.12; z = −1.58 [P = .113]) for serious adverse events was observed. No significant publication bias was noticed. The quality of the evidence was rated as high. Adjunct SDAM increased remission in patients and had no significant effect on serious adverse events compared to placebo. Therefore, we conclude that SDAM drugs can be an effective and safe antidepressant augmentation strategy in patients with major depressive disorder.
Association study of miR‐149, miR‐196a2, and miR‐499a polymorphisms with coronary artery aneurysm of Kawasaki disease in southern Chinese population
Authors: Fu Lanyan , Xu Yufen , Yu Hongyan , Pi Lei , Li Jinqing , Zhou Huazhong , Zhang Li , Zhang Tingfang , Che Di , Gu Xiaoqiong
Published: December 2021

Background

Accumulating evidence suggests that several microRNA (miRNA) polymorphisms are closely associated with disease susceptibility or progression, such as in Kawasaki disease (KD). Our previous studies revealed the association of miR‐149 rs2292832 T>C and miR‐196a2 rs11614913 C>T polymorphisms with KD susceptibility. The present study further focused on the relationship between three miRNA polymorphisms (miR‐149 rs2292832 T>C, miR‐196a2 rs11614913 C>T and miR‐499a rs3746444 A>G) and the risk of coronary artery aneurysm (CAA) in southern Chinese KD patients.

Methods

We evaluated 318 KD patients with CAAs and 784 patients without CAAs. TaqMan assays were used to estimate genotyping and analyze the relationship between miRNA polymorphisms (miR‐149 rs2292832 T>C, miR‐196a2 rs11614913 C>T and miR‐499a rs3746444 A>G) and risk associations of CAA by odds ratios (ORs) and 95% confidence intervals (CIs).

Results

We found that the miR‐149 rs2292832 TC/CC genotype increased the CAA risk (adjusted OR = 1.53, 95% CI = 1.15–2.03, p = 0.003 for TC, adjusted OR = 1.63, 95% CI = 1.08–2.47, p = 0.021 for CC), whereas the miR‐499a rs3746444 AG genotype decreased the CAA risk in KD patients (adjusted OR = 0.33, 95% CI = 0.25–0.45 p ≤ 0.001). Moreover, patients carrying two or three of these single nucleotide polymorphism (SNP) genotypes (rs2292832 TC/CC and rs11614913 TT and rs3746444 AA) had a higher risk for CAA than those who harbored only zero or one of these SNP genotypes.

Conclusions

Our results demonstrated that the miR‐149 rs2292832 T>C polymorphism increased the risk of CAA in KD patients and that the miR‐499a rs3746444 A>G polymorphism decreased the risk of CAA in KD patients. Further studies with larger sample sizes and different centers are needed to confirm the findings of the present study.
Poly(N‐vinyl‐2‐pyrrolidone)‐supported ferric chloride: An effective reusable heterogeneous catalyst for one‐pot synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones/thiones via three‐component Biginelli reaction
Authors: Rahmatpour Ali , Donyapeyma Ghazaleh
Published: December 2021

An environmentally benign three‐component Biginelli protocol for the one‐pot synthesis of substituted 3,4‐dihydropyrimidin‐2(1H)‐ones/thiones using an accessible, nontoxic, easy to handle, and recoverable macromolecular Lewis acidic catalyst is developed. N,N′‐methylene bis‐acrylamide‐cross‐linked poly(N‐vinyl‐2‐pyrrolidone) (MBA‐PVNP) as beads was used as a support for ferric chloride, resulting in a heterogeneous and reusable catalyst. The reusability test of the heterogenized version of ferric chloride, PNVP/FeCl3 ascertained that the obtained catalyst can be easily separated from the reaction mixture by filtration and reused several times with no great decline of activity.