bluuebunny/crossref_metadata_2025 huggingface dataset:
Assessment of the Effect of Different Irrigation Regimes on Pod Yield, Water Requirement & Productivity and Economics of Groundnut Varieties under the Southern Telangana Zone, India
Authors: Bhargavi A. Udaya , Kumar K. Avil , Neelima T. L. , Veeranna J.
Published: October 2022

The research was conducted at the Regional Agricultural Research Station, Palem during yasangi (rabi) 2020-21 to assess the impact of irrigation regimes on yield, water productivity, and economics of groundnut varieties. The experiment was laid out in a split plot design and comprising of three irrigation levels viz., irrigation at IW/CPE ratios of 1.0 (I1), 0.8 (I2), and 0.6 (I3), as main treatments and four groundnut varieties viz., K-6, GJG-32, KDG-128 and K-9 as sub treatments and replicated thrice. The soil was sandy clay loam having PH 7.3, available N, P, and K of 195, 35.8, and 87.36 kg ha-1, respectively. The highest pod yield of 2278 kg ha-1 and lowest pod yield of 1842 kg ha-1 could be obtained at the IW/CPE of 1.0 and 0.6 respectively requiring 677.7 ha.mm/ha and 450.7 ha.mm/ha of irrigation water respectively. There was no significant difference in gross returns, net returns, and B: C ratios recorded with irrigation at 1.0 IW/CPE ratio (Rs 126989 ha-1, Rs 47607 ha-1, and 1.60, respectively) and 0.8 IW/CPE and significantly lower with 0.6 IW/CPE ratio (Rs.102673 ha-1, Rs. 28311 ha-1 and 1.38, respectively). It can be concluded that K-6 or K-9 varieties can be grown during yasangi (rabi) with IW/CPE ratio of 0.8 or IW/CPE ratio of 1.0 as per irrigation water availability for higher water productivity and net returns.
Study of Catalytic Properties of the HoxMg1-xAl2O4 Modified HZSM-5 Zeolite in Conversion of Methanol to C2-C4 Alkenes and p-Xylene
Authors: Makhmudova Natavan I. , Mammadov Eyyub S. , Kerimli Fuad Sh. , Ilyasli Teymur M. , Akhmedova Nargiz Firudin , Mammadov Sabit E.
Published: October 2022

Selective conversion of methanol to C2-C4 alkenes and p-xylene is one of the appealing chemical routes. Currently, there are no effective catalysts for the co-production of C2-C4 alkenes and p-xylene from methanol. To date, modified medium-pore ZSM-5 zeolites are considered one of the excellent candidates for the development of selective catalysts for the conversion of methanol to lower alkenes and aromatic hydrocarbons. In this paper, nanosized (30-33nm) powders of HoхMg1-хAl2O4 spinel structure were obtained by the method of combustion of nitrate solutions of aluminium, magnesium, holmium, diethylmalonate and hydrazine monohydrate with the further calcination of nanopowders at 1000 °C. Obtained nanopowders used in the preparation of a solid-phase catalytic composition of HoхMg1-хAl2O4-HZSM-5. Various physico-chemical properties of the catalytic composition were investigated using X-ray diffraction (XRD), pyridine adsorption (BİO-RAD FTS 3000 MX) and low-temperature nitrogen adsorption (BET) techniques. The textural properties and acidity of the catalysts were altered by adjusting the nanopowder concentration (1.0-5.0 wt.%) in the catalytic composition. The conversion of methanol in the presence of the catalytic compositions was carried out in flow-type fixed-bed catalytic reactor at 400 °C, in the presence of nitrogen carrier gas with 1.0 h-1 flow rate. A correlation between the selectivity to C2-C4 alkenes and p-xylene with a ratio of Lewis (L) and Brønsted (B) acid sites and the volume of the catalyst pore, the amount of the modifier in the catalytic system has been established. As the amount of HoхMg1-хAl2O4 nanopowder increases, the ratio of B/L acid sites and the volume of the catalyst pore decrease, which play a significant role in the increase of the selectivity to C2-C4 alkenes and p-xylene. Maximum yield of C2-C4 alkenes (31.6%) and selectivity to p-xylene (80.5%) is achieved on a catalytic composition containing 5.0 wt.% HoxMg1-xAl2O4. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).
Misrepresentation and Nonadherence Regarding COVID-19 Public Health Measures
Authors: Levy Andrea Gurmankin , Thorpe Alistair , Scherer Laura D. , Scherer Aaron M. , Drews Frank A. , Butler Jorie M. , Burpo Nicole , Shoemaker Holly , Stevens Vanessa , Fagerlin Angela
Published: October 2022

Importance

The effectiveness of public health measures implemented to mitigate the spread and impact of SARS-CoV-2 relies heavily on honesty and adherence from the general public.

Objective

To examine the frequency of, reasons for, and factors associated with misrepresentation and nonadherence regarding COVID-19 public health measures.

Design, Setting, and Participants

This survey study recruited a national, nonprobability sample of US adults to participate in an online survey using Qualtrics online panels (participation rate, 1811 of 2260 [80.1%]) from December 8 to 23, 2021. The survey contained screening questions to allow for a targeted sample of one-third who had had COVID-19, one-third who had not had COVID-19 and were vaccinated, and one-third who had not had COVID-19 and were unvaccinated.

Main Outcomes and Measures

The survey assessed 9 different types of misrepresentation and nonadherence related to COVID-19 public health measures and the reasons underlying such behaviors. Additional questions measured COVID-19–related beliefs and behaviors and demographic characteristics.

Results

The final sample included 1733 participants. The mean (SD) participant age was 41 (15) years and the sample predominantly identified as female (1143 of 1732 [66.0%]) and non-Hispanic White (1151 of 1733 [66.4%]). Seven hundred twenty-one participants (41.6%) reported misrepresentation and/or nonadherence in at least 1 of the 9 items; telling someone they were with or about to be with in person that they were taking more COVID-19 preventive measures than they actually were (420 of 1726 [24.3%]) and breaking quarantine rules (190 of 845 [22.5%]) were the most common manifestations. The most commonly endorsed reasons included wanting life to feel normal and wanting to exercise personal freedom. All age groups younger than 60 years (eg, odds ratio for those aged 18-29 years, 4.87 [95% CI, 3.27-7.34]) and those who had greater distrust in science (odds ratio, 1.14 [95% CI, 1.05-1.23]) had significantly higher odds of misrepresentation and/or nonadherence for at least 1 of the 9 items.

Conclusions and Relevance

In this survey study of US adults, nearly half of participants reported misrepresentation and/or nonadherence regarding public health measures against COVID-19. Future work is needed to examine strategies for communicating the consequences of misrepresentation and nonadherence and to address contributing factors.
Trends in Dispensing of Controlled Medications for US Adolescents and Young Adults, 2008 to 2019
Authors: Toce Michael S. , Michelson Kenneth A. , Chen Krista Y. , Hudgins Joel D. , Olson Karen L. , Bourgeois Florence T.
Published: October 2022

This cohort study examines trends from 2008 to 2019 in dispensations of controlled medications to US adolescents and young adults.
Disulfide bond formation and redox regulation in the Golgi apparatus
Authors: Reznik Nava , Fass Deborah
Published: October 2022

Formation of disulfide bonds in secreted and cell‐surface proteins involves numerous enzymes and chaperones abundant in the endoplasmic reticulum (ER), the first and main site for disulfide bonding in the secretory pathway. Although the Golgi apparatus is the major station after the ER, little is known about thiol‐based redox activity in this compartment. QSOX1 and its paralog QSOX2 are the only known Golgi‐resident enzymes catalyzing disulfide bonding. The localization of disulfide catalysts in an organelle downstream of the ER in the secretory pathway has long been puzzling. Recently, it has emerged that QSOX1 regulates particular glycosyltransferases, thereby influencing a central activity of the Golgi. Surprisingly, a few important disulfide‐mediated multimerization events occurring in the Golgi were found to be independent of QSOX1. These multimerization events depend, however, on the low pH of the Golgi lumen and secretory granules. We compare and contrast disulfide‐mediated multimerization in the ER vs. the Golgi to illustrate the variety of mechanisms controlling covalent supramolecular assembly of secreted proteins.
Congruence among multiple indices of habitat preference for species facing human‐induced rapid environmental change: A case study using the Brewer's sparrow
Authors: Carlin Max , Chalfoun Anna D.
Published: October 2022

Accurate evaluations of habitat preference are key to understanding optimal conditions for wildlife survival and reproduction. Habitat selection, however, usually is evaluated using a single index of preference, and congruence among multiple, relevant indices of preference is examined rarely.

We assessed the concordance between patterns of habitat preference using three different indices of breeding site preference in a migratory songbird. Specifically, we compared the chronology of territorial establishment, pair formation and reproductive initiation of the Brewer's sparrow (Spizella breweri) along a gradient of surface disturbance associated with natural gas development in Wyoming, USA during 2019.

We expected all three indices to demonstrate a preference for breeding sites with less surface disturbance, where reproductive success typically is higher. By contrast, all indices suggested suboptimal preference with respect to surface disturbance, with some discrepancy among them. The chronology of settlement and pairing did not vary across the disturbance gradient, whereas nest initiation tended to occur earlier at sites with more disturbance.

If the pattern of suboptimal selection of breeding sites that we identified is generalizable across other populations of migratory birds affected by energy development, the resultant lower fitness in those areas may exacerbate population declines.

Our results suggest that traditional, single‐index approaches to the study of habitat selection, if chosen carefully, may provide adequate inference on habitat preferences. Different metrics, however, can lead to at least subtle differences in patterns of habitat selection. The simultaneous examination of multiple indices of preference across a diversity of systems would help clarify the contexts under which preference metrics can become decoupled.
A Wide Bandgap Halide Perovskite Based Self‐Powered Blue Photodetector with 84.9% of External Quantum Efficiency
Authors: Yun Yeonghun , Han Gill Sang , Park Gyu Na , Kim Jihyun , Park Jinhong , Vidyasagar Devthade , Jung Jina , Choi Won Chang , Choi Young Jin , Heo Kwang , Kang Joohoon , Park Ji‐Sang , Jung Hyun Suk , Lee Sangwook
Published: October 2022

A self‐powered, color‐filter‐free blue photodetector (PD) based on halide perovskites is reported. A high external quantum efficiency (EQE) of 84.9%, which is the highest reported EQE in blue PDs, is achieved by engineering the A‐site monovalent cations of wide‐bandgap perovskites. The optimized composition of formamidinium (FA)/methylammonium (MA) increases the heat of formation, yielding a uniform and smooth film. The incorporation of Cs+ ions into the FA/MA composition suppresses the trap density and increases charge‐carrier mobility, yielding the highest average EQE of 77.4%, responsivity of 0.280 A W−1, and detectivity of 5.08 × 1012 Jones under blue light. Furthermore, Cs+ improves durability under repetitive operations and ambient atmosphere. The proposed device exhibits peak responsivity of 0.307 A W−1, which is higher than that of the commercial InGaN‐based blue PD (0.289 A W−1). This study will promote the development of next‐generation image sensors with vertically stacked perovskite PDs.
Direct Asymmetric α‐C−H Addition of N‐unprotected Propargylic Amines to Trifluoromethyl Ketones by Carbonyl Catalysis
Authors: Ji Pengwei , Liu Xiaopei , Xu Jiwei , Zhang Xu , Guo Jianhua , Chen Wen‐Wen , Zhao Baoguo
Published: October 2022

Direct asymmetric functionalization of the inert α C−H bonds of N‐unprotected propargylic amines is a big challenge in organic chemistry, due to the low acidity (pKa≈42.6) of the α C−H bonds and interruption of the nucleophilic NH2group. By using a chiral pyridoxal as carbonyl catalyst, we have successfully realized direct asymmetric α‐C−H addition of N‐unprotected propargylic amines to trifluoromethyl ketones, producing a broad range of chiral alkynyl β‐aminoalcohols in 54–84 % yields with excellent stereoselectivities (up to 20 : 1 dr and 99 % ee). The α C−H bonds of propargylic amines are greatly activated by the pyridoxal catalyst via the formation of an imine intermediate, resulting in the increase of acidity by up to 1022 times (from pKa 42.6 to pKa 20.1), which become acidic enough to be deprotonated under mild conditions for the asymmetric addition. This work presented an impressive example for asymmetric functionalization of inert C−H bonds enabled by an organocatalyst.
Lichtgesteuerte Konstruktion und Zerstörung: Schaltung zwischen zwei unterschiedlich zusammengesetzten käfigartigen Komplexen
Authors: Hugenbusch Daniel , Lehr Marc , von Glasenapp Jan‐Simon , McConnell Anna J. , Herges Rainer
Published: October 2022

Wir berichten über zwei regioisomere Diazocinliganden 1 und 2, die beide mit violettem und grünem Licht zwischen den E‐ und Z‐Konfigurationen geschaltet werden können. Die Selbstorganisation der vier Spezies (1‐Z, 1‐E, 2‐Z, 2‐E) mit CoII‐Ionen wurde nach Änderung der Koordinationsvektoren in Abhängigkeit von der Ligandenkonfiguration (E vs. Z) und dem Regioisomer (1 vs. 2) untersucht. Mit 1‐Z bildet sich Co2(1‐Z)3, während mit 2‐Z ein undefiniertes Gemisch verschiedener Spezies (Oligomere) beobachtet wurde. Bei Belichtung der E‐Konfigurationen mit 385 nm wurde die gegenteilige Situation beobachtet, wobei 1‐E Oligomere und 2‐E den Komplex Co2(2‐E)3 bildete. Der lichtgesteuerte Abbau/Aufbau wurde in einem Ligandenverdrängungsexperiment mit substöchiometrischen Mengen von CoII‐Ionen demonstriert. Die abwechselnde Bestrahlung mit violettem und grünem Licht führte zu einer reversiblen Umwandlung zwischen Co2(1‐Z)3 und Co2(2‐E)3 über mehrere Zyklen hinweg ohne signifikante Ermüdung.
Directing Group‐Free Formal Suzuki–Miyaura Coupling of Simple Ketones Enabled by Activation of Unstrained C−C Bonds
Authors: Huang Jiangkun , Yan Xufei , Xia Ying
Published: October 2022

The use of ketones as electrophiles to couple with arylboronic acid derivatives via C−C bond activation has become a significant progress in the area of Suzuki–Miyaura coupling (SMC) reaction, in which a permanent or temporary directing group is often required to promote the activation of the unstrained C−C bond via oxidative addition. Herein, we disclosed the first example of directing group free formal SMC reaction of simple ketones with arylboronates via Rh‐catalyzed unstrained C−C bond activation. A wide range of simple ketones, including aryl alkyl ketones, diaryl ketones and aryl perfluoroalkyl ketones, can serve as electrophiles to participate in the SMC reaction with aryl or perfluoroalkyl as the leaving group. The key to the success of this reaction is by means of nucleophilic addition/β‐carbon elimination sequence that can activate the unstrained ketone carbonyl C−C bond without the assistance of directing group.
Preparation and properties of polyimide dielectric nanocomposites containing polyvinylpyrrolidone chemically functionalized barium titanate by in‐situ synthesis compounding
Authors: Yang Shang Ke , Zhang Zhao Xin , Zhang Ai Ping , Lin Hai Lan , Zhang Xun Tao , Xiao Liu Xin , Bian Jun , Chen Dai Qiang
Published: October 2022

This work employed polymer active agent polyvinylpyrrolidone (PVP) treated barium titanate (BT) nanoparticles (PVP@BT) as functional nanofillers to fill polyimide (PI) matrix to fabricate PI nanocomposite films. The microstructure, dielectric properties, and heat resistance of PI, PI/BT, and PI/PVP@BT dielectric nanocomposite films were investigated. Fourier transform infrared spectrometer (FTIR) indicated that PVP has been successfully coated on the surface of BT nanoparticles. Due to the enhanced aggregation of monomers on the PVP@BT nanoparticles, higher molecular weight and viscosity of PI/PVP@BT nanocomposite films were achieved. Compared with PI/BT nanocomposite films, the dispersion of PVP@BT nanoparticles in PI/PVP@BT nanocomposite films was better, as verified by field emission scanning electron microscope and high‐resolution transmission electron microscopy. Filling a small amount of PVP@BT nanoparticles into the PI matrix improved the dielectric properties of the resultant nanocomposite films. The dielectric constant of the nanocomposite films with 10 wt% filler loading was up to 7.1 at 1000 Hz, which was 2.5 times higher than that of pure PI (2.9). PI nanocomposite film dielectric loss was generally lower than 0.015. Thermogravimetric analysis (TGA) tests verified that both pure PI and PI nanocomposite films showed excellent thermal stability. This work can be expected to provide a new strategy for designing and manufacturing PI dielectric nanocomposite films for energy storage applications.
Player profiles for game‐based applications in engineering education
Authors: Vergara Diego , Antón‐Sancho Álvaro , Fernández‐Arias Pablo
Published: October 2022

The use of digital learning environments in higher education has led to design methodological strategies, like gamification, adapted to computer‐based learning. The effectiveness of gamification depends on the adaptation of the methodology to the player's profile. Four types of player profiles (Explorer, Killer, Socialized, and Achiever) are established according to the Bartle classification. In this article, quantitative research is carried out on the player profile and the one considered best for learning engineering professors. Sociological and academic aspects that influence player profile choices are also identified. A descriptive and inferential analysis of the answers given by a population of 532 engineering professors —who attended a training course on gamification in digital environments—to a survey designed by the authors was carried out. The results reveal that most engineering professors are Explorers and this is also the player profile considered best for learning, although there is a gap between the own player profile and the choice of the most effective one. The player profile shown here to be the most frequent among engineering professors differs from that attributed to students in the literature, which is Achiever. Gaps by gender, age, teaching experience, and university tenure are also identified. Universities are recommended to strengthen professor training to design personalized game‐based computing environments and to cater to differences due to several sociological and academic aspects.
A signature based on NKG2D ligands to predict the recurrence of hepatocellular carcinoma after radical resection
Authors: Chen Dongbo , Gao Jie , Ren Liying , Chen Pu , Yang Yao , She Shaoping , Xie Yong , Liao Weijia , Chen Hongsong
Published: October 2022

Introduction

Due to the high recurrence, the HCC prognosis remains poor. Yet, the biomarkers for predicting the recurrence of high‐risk patients are currently lacking. We aimed to develop a signature to predict the recurrence of HCC based on NKG2D ligands.

Methods

The multivariate Cox proportional hazards regression was used to select recurrence‐related variables of NKG2D ligands in HCC patients from The Cancer Genome Atlas (TCGA). HCC patients from the OEP000321 dataset and Guilin cohort were used to validate the predictive signature. The mRNA expression of NKG2D ligands was measured by QRT‐PCR. Immunohistochemistry analysis of HCC tissue microarray samples was used to identify the expression of NKG2D ligands.

Results

In this study, NKG2D ligands expression in the mRNA and protein level was both abnormally expressed in HCC and associated with recurrence‐free survival (RFS). Then, the recurrence‐related variables of NKG2D ligands in HCC were selected by the multivariate Cox proportional hazards regression. Among the eight NKG2D ligands, MICA (HR = 1.347; 95% CI = 1.012–1.793; p = 0.041), ULBP3 (HR = 0.453; 95% CI = 0.231–0.889; p = 0.021) and ULBP5 (HR = 3.617; 95% CI = 1.819–7.194; p < 0.001) were significantly correlated with RFS in the TCGA‐LIHC cohort. Then, the signature was constructed by the three NKG2D ligands. The predictive effectiveness of this signature was also validated in the OEP000321 dataset and Guilin cohort. Further, HCC patients were classified into low‐risk and high‐risk subgroups by the predictive score. Compared with the low‐risk group, the high‐risk group had poor RFS in both training and validation cohorts. Importantly, compared with the low‐risk patients with the G1‐G2 stage, the levels of infiltrated NK‐activated cells and NKG2D expression were both lower in the high‐risk patients.

Conclusions

The signature based on MICA, ULBP3, and ULBP5 could predict HCC recurrence.
Clinical results of active surveillance for extra‐abdominal desmoid‐type fibromatosis
Authors: Sakai Tomohisa , Nishida Yoshihiro , Ito Kan , Ikuta Kunihiro , Urakawa Hiroshi , Koike Hiroshi , Imagama Shiro
Published: October 2022

Background

The treatment of choice for desmoid‐type fibromatosis (DF) has been changed to active surveillance (AS). However, few studies have reported clinical outcomes of AS modality in Asian countries. This study aimed to clarify the significance of AS as a DF treatment modality.

Methods

A total of 168 lesions from 162 patients with extra‐abdominal DF were included. The mean age at diagnosis was 39 years (1–88 years), and the median maximum tumor diameter at the first visit was 64.1 mm (13.2–255.8 mm). The clinical outcomes of AS and the risk factors requiring active treatment (AT) (defined as an event) from AS modality were investigated.

Results

Of the 168 lesions, 94 (56%) were able to continue AS, with a 5‐year event‐free survival of 54.8%. Of the 68 lesions with PD, 21 (30.9%) lesions were able to continue AS. Neck location (p = 0.043) and CTNNB1 S45F mutation (p = 0.003) were significantly associated with the transition to AT, and S45F mutation was a significant factor associated with the transition to AT by multivariate analysis (hazard ratio: 1.96, p = 0.048). AT outcomes after AS were evaluable in 65 lesions, and 49 (75%) lesions did not require a transition to a second AT.

Conclusions

AS was revealed as an effective treatment modality. The transition to AT needs to be considered for neck location and CTNNB1 S45F mutation DF. Good results can be obtained by selecting a treatment method that considers the tumor location even in cases that require intervention.
Chiral Naphthalenediimides with High‐Efficiency Fluorescence and Circularly Polarized Luminescence in the Solid State for the Application in Organic Optoelectronics
Authors: Gao Yuping , Wang Liangpeng , Ma Xiaoye , Jin Rizhe , Kang Chuanqing , Gao Lianxun
Published: October 2022

Naphthalenediimides (NDIs) have been extensively studied due to their tunable luminescent properties. However, generally, the monomers or aggregates of non‐core substituted NDIs exhibit low fluorescence quantum yields (ΦFL<10 %) in the solid state, which limit their applications as light‐emitting materials and render their chiral species unsuitable for circularly polarized luminescence (CPL). Herein, a series of non‐core substituted chiral NDIs that exhibit high luminous efficiencies (ΦFL up to 56.8 % for racemate and 36.5 % for enantiomer) and a strong CPL behavior in the solid state is reported. These significant improvements are attributed to the unique molecular conformation of the chiral NDIs and the formation of distinctive discrete dimers. The structures of the NDIs were significantly simpler and more accessible than those of other NDIs. The findings evidence that non‐core substituted NDIs can exhibit strong fluorescence in the solid state and provide a new pathway to improve photophysical properties of NDIs.
Dithiolopyrrolones are Prochelators that are Activated by Glutathione
Authors: Albini Francesca , Bormann Stefan , Gerschel Philipp , Ludwig Veza A. , Neumann Wilma
Published: October 2022

Dithiolopyrrolones (DTPs), such as holomycin, are natural products that hold promise as scaffolds for antibiotics as they exhibit inhibitory activity against antibiotic‐resistant pathogens. They consist of a unique bicyclic core containing a disulfide that is crucial for their biological activity. Herein, we establish the DTPs as prochelators. We show that the disulfides are reduced at cellular gluathione levels. This activates the drugs and initiates interactions with targets, particularly metal coordination. In addition, we report an expedient synthesis for the DTPs thiolutin and aureothricin, providing facile access to important natural DTPs and derivatives thereof.
Organic Crystals with Response to Multiple Stimuli: Mechanical Bending, Acid‐Induced Bending and Heating‐Induced Jumping
Authors: Wu Wenbo , Chen Kui , Zhang Xiunan , Wang Ting , Li Shuyu , Zhao Hongtu , Zhou Lina , Huang Xin , Hao Hongxun
Published: October 2022

Multiple stimuli‐responsive molecular crystals are attracting extensive attentions due to their potential as smart materials, such as molecular machines, actuators, and sensors. However, the task of giving a single crystal multiple stimuli‐responsive properties remains extremely challenging. Herein, we found two polymorphs (Form O and Form R) of a Schiff base compound, which could respond to multiple stimuli (external force, acid, heat). Form O and Form R have different elastic deformability, which can be attributed to the differences in the molecular conformation, structural packing and intermolecular interactions. Moreover, both polymorphs exhibit reversible bending driven by volatile acid vapor, which we hypothesize is caused by reversible protonation reaction of imines with formic acid. In addition, jumping can be triggered by heating due to the significant anisotropic expansion. The integration of reversible bending and jumping into one single crystal expands the application scope of stimuli‐responsive crystalline materials.
A Hydride‐Substituted Homoleptic Silylborate: How Similar is it to its Diborane(6)‐Dianion Isostere?
Authors: Gilmer Jannik , Bolte Michael , Virovets Alexander , Lerner Hans‐Wolfram , Fantuzzi Felipe , Wagner Matthias
Published: October 2022

The B‐nucleophilic 9H‐9‐borafluorene dianion reacts with 9‐chloro‐9‐silafluorene to afford air‐ and moisture‐stable silylborate salts M[Ar2(H)B−Si(H)Ar2] (M[HBSiH], M=Li, Na). Li[HBSiH] and Me3SiCl give the B−pyridine adduct Ar2(py)B−Si(H)Ar2((py)BSiH) or the chlorosilane Li[Ar2(H)B−Si(Cl)Ar2] (Li[HBSiCl]) in C6H6‐pyridine or THF. In both cases, the first step is H−abstraction at the B center. The resulting free borane subsequently binds a py or thf ligand. While the py adduct is stable at room temperature, the thf adduct undergoes a 1,2‐H shift via the cyclic B(μ‐H)Si intermediateBHSi, which is afterwards attacked at the Si atom by a Cl−ion to give Li[HBSiCl]. DFT calculations were employed to support the proposed reaction mechanism and to characterize the electronic structure ofBHSi. Treatment of Li[HBSiCl] with the N‐heterocyclic carbene IMe introduces the neutral donor at the Si atom and leads to Ar2(H)B−Si(IMe)Ar2(HBSi(IMe)), a donor‐acceptor‐stabilized silylene.
Bronchial hyperresponsiveness and asthma during oral immunotherapy for egg or peanut allergy in children
Authors: Burman Janne , Palosuo Kati , Pelkonen Anna , Malmberg Pekka , Remes Sami , Kukkonen Kaarina , Mäkelä Mika J.
Published: October 2022

Background

Bronchial hyperresponsiveness (BHR) and asthma are frequently present in children with food allergy. We assessed BHR in children receiving oral immunotherapy (OIT) for persistent egg or peanut allergy and examined whether OIT affects asthma control.

Methods

Methacholine challenge testing was performed in 89 children with persistent egg or peanut allergy diagnosed by double‐blind, placebo‐controlled food challenge and 80 control children without food allergy. Of the 89 food‐allergic children, 50 started OIT for egg allergy and 39 for peanut allergy. Sensitization to aeroallergens was evaluated by skin prick testing. Forty of the 89 children with regular controller treatment for asthma underwent methacholine challenge testing and 34 measurement of exhaled nitric oxide (FeNO) at baseline and after 6–12 months of OIT.

Results

Methacholine challenge testing revealed significant BHR in 29/50 children (58%) with egg allergy, 15/39 children (38%) with peanut allergy, and 6/80 controls (7.5%). The mean cumulative dose of methacholine causing a 20% fall in FEV1 differed significantly between the egg and peanut‐allergic versus the control children (1009 μg, 1104 μg, and 2068 μg, respectively, p < 0.001). Egg or peanut OIT did not affect lung function, the degree of BHR or FeNO levels in children with asthma and had no adverse effect on asthma control. Lung function or BHR did not associate with the OIT outcome.

Conclusion

BHR was significantly more frequent in children with persistent egg or peanut allergy than in children without food allergy. Oral immunotherapy did not increase BHR and was safe for children on regular asthma medication.
Adult spinal Dmrt3 neurons receive direct somatosensory inputs from ipsi‐ and contralateral primary afferents and from brainstem motor nuclei
Authors: Vieillard Jennifer , Franck Marina C. M. , Hartung Sunniva , Jakobsson Jon E. T. , Ceder Mikaela M. , Welsh Robert E. , Lagerström Malin C. , Kullander Klas
Published: October 2022

In the spinal cord, sensory‐motor circuits controlling motor activity are situated in the dorso–ventral interface. The neurons identified by the expression of the transcription factor Doublesex and mab‐3 related transcription factor 3 (Dmrt3) have previously been associated with the coordination of locomotion in horses (Equus caballus, Linnaeus, 1758), mice (Mus musculus, Linnaeus, 1758), and zebrafish (Danio rerio, F. Hamilton, 1822). Based on earlier studies, we hypothesized that, in mice, these neurons may be positioned to receive sensory and central inputs to relay processed commands to motor neurons. Thus, we investigated the presynaptic inputs to spinal Dmrt3 neurons using monosynaptic retrograde replication‐deficient rabies tracing. The analysis showed that lumbar Dmrt3 neurons receive inputs from intrasegmental neurons, and intersegmental neurons from the cervical, thoracic, and sacral segments. Some of these neurons belong to the excitatory V2a interneurons and to plausible Renshaw cells, defined by the expression of Chx10 and calbindin, respectively. We also found that proprioceptive primary sensory neurons of type Ia2, Ia3, and Ib, defined by the expression of calbindin, calretinin, and Brn3c, respectively, provide presynaptic inputs to spinal Dmrt3 neurons. In addition, we demonstrated that Dmrt3 neurons receive inputs from brain areas involved in motor regulation, including the red nucleus, primary sensory–motor cortex, and pontine nuclei. In conclusion, adult spinal Dmrt3 neurons receive inputs from motor‐related brain areas as well as proprioceptive primary sensory neurons and have been shown to connect directly to motor neurons. Dmrt3 neurons are thus positioned to provide sensory–motor control and their connectivity is suggestive of the classical reflex pathways present in the spinal cord.
Varying thin filament activation in the framework of the Huxley'57 model
Authors: Kimmig François , Caruel Matthieu , Chapelle Dominique
Published: October 2022

Muscle contraction is triggered by the activation of the actin sites of the thin filament by calcium ions. It results that the thin filament activation level varies over time. Moreover, this activation process is also used as a regulation mechanism of the developed force. Our objective is to build a model of varying actin site activation level within the classical Huxley'57 two‐state framework. This new model is obtained as an enhancement of a previously proposed formulation of the varying thick filament activation within the same framework. We assume that the state of an actin site depends on whether it is activated and whether it forms a cross‐bridge with the associated myosin head, which results in four possible states. The transitions between the actin site states are controlled by the global actin sites activation level and the dynamics of these transitions is coupled with the attachment–detachment process. A preliminary calibration of the model with experimental twitch contraction data obtained at varying sarcomere lengths is performed.
The Diverse Modes of Oxygen Reactivity in Life & Chemistry
Authors: Stuhr Robin , Bayer Patrick , von Wangelin Axel Jacobi
Published: October 2022

Oxygen is a molecule of utmost importance in our lives. Beside its vital role for the respiration and sustaining of organisms, oxygen is involved in numerous chemical and physical processes. Upon combination of the different forms of molecular oxygen species with various activation modes, substrates, and reaction conditions an extremely wide chemical space can be covered that enables rich applications of diverse oxygenation processes. This Review provides an instructive overview of the individual properties and reactivities of oxygen species and illustrates their importance in nature, everyday life, and in the context of chemical synthesis.
A Highly Stable Ortho‐Ketoenamine Covalent Organic Framework with Balanced Hydrophilic and Hydrophobic Sites for Atmospheric Water Harvesting
Authors: Chen Liang‐Hui , Han Wang‐Kang , Yan Xiaodong , Zhang Jiangwei , Jiang Yuqin , Gu Zhi‐Guo
Published: October 2022

Atmospheric moisture is a sustainable clean water source that can solve the shortage of fresh water in arid areas. Herein a 2D covalent organic framework (COF‐ok) was reported as a promising porous sorbent for solar‐driven atmospheric water harvesting. COF‐ok with ortho‐ketoenamine linkage was extremely stable in harsh environment, including in boiling water, strong acids and bases. Because of the balanced hydrophilic and hydrophobic sites in channels, COF‐ok showed a high water uptake of 0.33 g g−1 at a low relative humidity of 34 % featuring a characteristic S‐shaped water sorption isotherm with low regeneration temperature (∼45 °C) and excellent cyclic stability. A laboratory‐scale water harvesting system could collect water of 161 g kg−1 under sunlight.
The potential application of event‐related potentials to enhance research on reward processes in eating disorders
Authors: Forester Glen , Schaefer Lauren M. , Dodd Dorian R. , Johnson Jeffrey S.
Published: October 2022

Objective

Reward‐related processes have been posited as key mechanisms underlying the onset and persistence of eating disorders, prompting a growing body of research in this area. Existing studies have primarily utilized self‐report, behavioral, and functional magnetic resonance imaging measures to interrogate reward among individuals with eating disorders. However, limitations inherent in each of these methods (e.g., poor temporal resolution) may obscure distinct neurocognitive reward processes, potentially contributing to underdeveloped models of reward dysfunction within eating disorders. The temporal precision of event‐related potentials (ERPs), derived from electroencephalography, may thus offer a powerful complementary tool for elucidating the neurocognitive underpinnings of reward. Indeed, a considerable amount of research in other domains of psychopathology (e.g., depression, substance use disorders), as well as studies investigating food reward among non‐clinical samples, highlights the utility of ERPs for probing reward processes. However, no study to date has utilized ERPs to directly examine reward functioning in eating disorders.

Methods

In this paper, we review evidence underscoring the clinical utility of ERP measures of reward, as well as a variety of reward‐related tasks that can be used to elicit specific ERP components with demonstrated relevance to reward processing. We then consider the ways in which these tasks/components may be used to help answer a variety of open questions within the eating disorders literature on reward.

Results/Discussion

Given the promise of ERP measures of reward to the field of eating disorders, we ultimately hope to spur and guide research in this currently neglected area.

Public Significance

Abnormalities in reward functioning appear to contribute to eating disorders. Event‐related potentials (ERPs) offer temporally precise measures of neurocognitive reward processing and thus may be important tools for understanding the relationship between reward and disordered eating. However, research in this area is currently lacking. This paper attempts to facilitate the use of ERPs to study reward among individuals with eating disorders by reviewing the relevant theories and methods.
Tolerogenic dendritic cells alleviate collagen‐induced arthritis by forming microchimerism and affecting the expression of immune checkpoint molecules
Authors: Wan Xiufang , Bao Lunmin , Ma Guilan , Long Tiaoyu , Li Honghong , Zhang Yundong , Jiang Hongmei
Published: October 2022

Tolerogenic dendritic cells (tolDCs) have the potential to treat rheumatoid arthritis (RA) by inducing immune tolerance. However, the mechanism of intervention needs further study. Here, we investigated whether tolDCs formed microchimerism and their effect on the expression of immune checkpoint molecules after infusion of tolDCs into rats with collagen‐induced arthritis (CIA). TolDCs derived from male SD rats were labeled with fluorescence and infused into female CIA rats. The fluorescence signals as well as the sex‐determining region of Y‐chromosome (SRY) gene revealed that tolDCs formed microchimerism in the mesenteric lymph nodes and ankle joints. We further explored the effect of tolDCs on the expression of immune checkpoint molecules in mesenteric lymph nodes and ankle joints. For stimulatory immune checkpoint molecules, the expressions of CD86 and CD40 decreased in mesenteric lymph nodes, and the expressions of CD40, CD40L, CD28, CD80, and CD86 also decreased in rat ankle joints. In contrast, the inhibitory immune checkpoint molecule PDL1 increased in mesenteric lymph nodes, and PD1, PDL1, and CTLA4 increased in ankle joints. In conclusion, our results suggested that intervention of tolDCs in CIA is associated with the formation of microchimerism and the effect on immune checkpoints.
A Remarkable Ring Opening Observed in the Reaction of Cyclopropyl Ferrocenyl Thioketone with Triiron Dodecacarbonyl Fe3(CO)12
Authors: Buday Philipp , Celeda Małgorzata , Görls Helmar , Mlostoń Grzegorz , Weigand Wolfgang
Published: October 2022

In continuation of the study focused on synthesis and structure of mimics of the active site of the [FeFe] hydrogenase enzyme, reaction of Fe3(CO)12 with cyclopropyl ferrocenyl thioketone 1 was carried out. Two different complexes with ring‐opened cyclopropyl fragments were isolated and identified as η4‐1‐thia‐1,3‐diene‐type mononuclear tricarbonyl iron complex 2 and η2‐acyl‐type hexacarbonyl diiron complex 3, respectively. Structures of crystalline products were unambiguously confirmed by single crystal X‐ray analysis. For the ring opening reaction of the cyclopropane moiety, leading to the formation of 2 and 3, a multistep radical mechanism was postulated. Electrochemical investigations of 3, being reminiscent of a [FeFe] hydrogenase mimic, were carried out at different scan rates.
Isomerism in Hexacoordinate Ti(IV) and Zr(IV) Complexes with a Tetradentate ONNO‐Schiff Base Ligand
Authors: Rezaei Kheirkhah Bahareh , Al‐Shboul Tareq M. A. , Pröhl Felix Edwin , Krieck Sven , Görls Helmar , Westerhausen Matthias
Published: October 2022

The reactions of [(thf)2TiCl4] with sodiated 2,2’‐bis[2‐hydroxy‐3,5‐di(tert‐butyl)benzylideneamino]‐1,1’‐biphenyl (1 a) and 2,2’‐bis[2‐hydroxy‐3,5‐di(tert‐butyl)benzylideneamino]‐4,4’‐dimethyl‐1,1’‐biphenyl (1 b) yield the corresponding Ti complexes 2 a and 2 b. Similarly, 1 a reacts with [(thf)2ZrCl4] to the corresponding Zr derivative 3. For 2 a, a mixture of cis‐β and trans isomers were observed in solution whereas the Zr congener exclusively forms the cis‐α form. Quantum chemical calculations verify that these isomers are the preferred molecular structures. The crystal structures of cis‐β isomeric 2 a and cis‐α isomeric 3 have been determined. Metalation of 1 a with Ti(NMe2)4 yields 2,2’‐bis[(2‐oxido‐3,5‐di(tert‐butyl)phenyl)‐dimethylaminomethylamino]‐1,1’‐biphenyl titanium(IV) (4) with a hexadentate ligand.
Nanoarchitectonics of High‐Performance Bis(triethoxysilyl)methane (BTESM) Hybrid‐Silica Membrane for Pervaporative Desalination Applications
Authors: Wang Jiaxuan , Yang Jianhua , Raza Waseem , Saulat Hammad , Ma Lei , Lu Jinming
Published: October 2022

As an emerging technology, desalination by pervaporation (PV) has excellent potential in freshwater supply from saline waters. However, the investigation of stable membrane materials needs still to address separation issues such as fouling in desalination applications. Ceramic membranes, especially hybrid‐silica membranes, possess the required properties for pervaporation desalination and remain potentially tolerant to various saline waters which conventional membranes cannot withstand. Herein, we report the preparation of a thin, short‐chain BTESM hybrid‐silica membrane on cheap macroporous alumina supports for desalination applications through pervaporation. The fabricated membrane delivered water flux of 9.1 kg m−2 h−1 and 6.7 kg m−2 h−1 at 60 °C for simulated and real based sampled seawater, respectively, with a high rejection of >99.5 %. The fabricated membrane delivers excellent separation for various salt ranges and different salt solutions, including KCl, MgCl2, and CaCl2. Further, the PV performance of fabricated membranes implies that hybrid silica based membranes can be potential candidates for commercial desalination markets.
Transfer learning with attention mechanism as predicting tool for dynamic adsorption of ammonia on MCM‐41 matrix materials
Authors: Zhu Ming , Gao Shenghan , Li Chengming , Wang Lei , Zhang Quanling
Published: October 2022

Gas adsorption is one important field of gas separation and air pollution control. The modeling prediction of dynamic adsorption can benefit process design and speed up material development. In this article, we try to propose intelligent model for modeling prediction of dynamic adsorption. Transfer learning with attention mechanism is utilized for the first time to capture flow details near breakthrough zone. The predicting target and training source are heterogeneous data from different materials and different operating conditions. The best predicting performance is obtained using one layer of long short‐term memory, linear activation function, and 70% training rate. Transfer learning with attention mechanism obtains the best predicting results for MgBr2/MCM‐41 adsorption at 200°C, 184 kPa is 7.032 × 10−8 in mean squared error (MSE). It also obtains the lowest predicting error of 4.609 × 10−8 in MSE, for predicting CaBr2/MCM‐41 adsorption at 200°C, 176 kPa. The results have proven the capability of modeling prediction of transfer learning with attention mechanism for dynamic ammonia adsorption on MCM‐41 matrix materials.
The clinical analysis of new‐onset status epilepticus
Authors: Deng Binlu , Dai Yuqian , Wang Qi , Yang Jie , Chen Xiang , Liu Ting‐Ting , Liu Jie
Published: October 2022

Objective

To investigate and analyze the etiology and prognosis of patients with new‐onset status epilepticus (NOSE).

Methods

We conducted a retrospective analysis of all adult patients (≧16 years old) who were admitted to Sichuan Provincial People's Hospital between January 2018 and December 2020 with status epilepticus (SE) and no prior epilepsy history.

Results

We collected data from 85 patients, aged from 16 to 90 years, of whom 49 were male and 36 were female. Fifty‐five of these cases (64.7%) were younger than 60 years of age. Acute symptomatic SE was mostly seen in the NOSE (53.9%), followed by unknown SE (25.9%), progressive SE (11.8%), and remote SE (9.4%). The differences in the etiology of NOSE between age groups were statistically significant (P < .05). For the young, the main etiology remained unknown (36.3%), followed by autoimmune‐related SE (16.4%); in the elderly, the primary etiology was central nervous system (CNS) infection (23.3%), followed by cerebrovascular disease (20%), and intracranial tumors (20%). Normal imaging was mostly seen in young people with NOSE (P < .001). Regarding outcome parameters and risk factors in patients with NOSE, adverse outcome was associated with age (OR = 3.5, 95% CI = 0.108–0.758, P = .012), co‐infection (OR = 4.5, 95% CI = 0.083–0.599, P = .003), and tracheal intubation (OR = 6.318, 95% CI = 0.060–0.204, P = .011).

Significance

In our cohort, intracranial tumors, CNS infections, and cerebrovascular disease were the predominant causes of NOSE in the elderly, while autoimmune encephalitis was the largest recognized cause of NOSE in young patients. In addition, imaging varies with age. According to the data, preventing infections may enhance patient prognosis because greater infection rates are connected with less favorable results. Meanwhile, age and mechanical ventilation are related to the prognosis of NOSE.
Channel head response to anthropogenic landscape modification: A case study from the North Carolina Piedmont, USA, with implications for water quality
Authors: Atkins Rachel M. , Wegmann Karl W. , Bohnenstiehl Del Wayne R.
Published: October 2022

European‐American settlement of the south‐eastern United States introduced agricultural practices that included extensive clearing of forested hillslopes to support food and cash‐crop agriculture. This land disturbance has long‐term effects on stream morphology by displacing channel heads down‐valley, impacting downstream sediment and nutrient supply as channel heads migrate back up‐valley towards their pre‐disturbance locations. This study investigates 40 stream channels in William B. Umstead State Park in the Piedmont of North Carolina using relationships between local slope and contributing drainage areas to predict channel head locations and compare these to their observed positions. Further, expected eroded sediment and nutrient contributions are quantified using migration distances and sampled soils near channel heads. Of the 40 investigated channel heads, 23 are located down‐valley from their predicted location by an average of 174.4 m ± 109.6 (1 − σ). Using this distance and average channel cross‐sectional area, 1.6 ± 1.4 m2 (1 − σ), the expected future erosion per channel is 282.6 ± 177.6 m3 (1 − σ). Drainage density was used to extrapolate volumes to the 23 km2 park using a conservative estimate that 50% of the first‐order channel heads will migrate up‐valley, implying an additional 90.4 ± 56.8 × 103 m3 (1 − σ) of sediment is expected to erode from the study area. Finally, scaling these volume estimates to sampled soil nutrient values indicates that approximately 1053 ± 662 t (68% confidence) of carbon, 51 ± 32 t of total nitrogen, and 15 ± 9 t of phosphorus are anticipated to enter the fluvial system in response to channel head migration from within the confines of this state park, representing only 1% of the land area in Wake County. These findings suggest that regional water quality challenges posed by suspended sediments and nutrients will persist for hundreds to perhaps thousands of years from non‐point sources as first‐order channels continue to erode headward towards their equilibrium landscape positions.