bluuebunny/crossref_metadata_2025 huggingface dataset:
Organic Charge‐Transfer Complex based Microstructure Interfaces for Solution‐Processable Organic Thin‐Film Transistors toward Multifunctional Sensing
Authors: Liu Zhiqi , Ju Zhengkun , Ma Shuang , Li Wenju , Chen Jinqiu , Yang Bo , Zhang Jing
Published: May 2023

The development of organic field‐effect transistor (OFET) based sensors is in high demand for flexible electronics. Herein, a new and feasible procedure to grow donor‐acceptor complex microstructures sandwiched between the semiconducting and insulating layers is reported. To realize a well‐distributed, uniform‐sized structure through coating on the gold patterned substrate, the dopping ratio of the organic donor‐acceptor complex in the host polymer is optimized. This method leads to one‐step fabrication of high‐performance semiconductor thin‐films and a microstructured binary system attached to it via successful phase separation. The OFET sensors prepared by this technique demonstrate ideal hole‐transport properties and good pressure response. In addition, the thermal‐sensitivity is also revealed, which enables the device architectures to be multifunctional. This work opens a new avenue to manufacture functional microstructure and flexible OFET based pressure sensors.
Hydrothermal Self‐Assembly of Gold Nanoparticles Embed on Carbon Felt for Effective Nitrogen Reduction
Authors: Zhang Wei , Wang Tianyi , Liu Chuangwei , Duan Chongxiong , Xiong Wei , Li Hao
Published: May 2023

Gold‐based electrocatalysts are potential candidates for electrocatalytic nitrogen reduction reaction (e‐NRR) application due to their high conductivity and low hydrogen evolution tendency. However, the role of nonmetallic Au surfaces is not widely studied. Herein, the self‐assembly of gold nanoparticles confined in carbon felts (Au NPs@CFs) containing two different states of Au is reported, showing effective e‐NRR performance. The effects of surfactant concentration on the morphology and electrochemical performance of the Au NPs are analyzed. X‐ray photoelectron spectroscopy indicates two valence states of Au (Au0 and Au3+) in Au NPs@CFs. Interestingly, it is found that the e‐NRR properties of Au NPs@CFs enhance with the increase of Au3+ content. A typical sample Au NPs@CF‐1.0 with the highest Au3+ content exhibits the best e‐NRR performance (NH3 yield of 66.1 μg h−1 mg−1cat. and Faradaic efficiency of 24.9% at −0.3 V vs reversible hydrogen electrode), which, in part due to the presence of Au3+, is conducive to nitrogen adsorption. Theoretical calculation results find that a stable Au3+ surface can adsorb N2 strongly, which in turn can lead to energetically favorable formation of ammonia. This study provides new insights into the relation between oxidation states and performance of gold‐based electrocatalyst with high e‐NRR performance.
Amyloid‐β is a cytokine
Authors: Weaver Donald F.
Published: May 2023

The role of amyloid‐β (Aβ) peptide in human physiology and pathology remains an unresolved subject of study; Aβ’s role in Alzheimer's disease (AD) is particularly controversial. However, before we can more fully appreciate Aβ’s role in AD, an understanding of its normal physiological role(s) must first be attained. This perspective appraises the current literature and concludes that Aβ is a cytokine. This conclusion was arrived at based on a comprehensive listing of 30 characteristic defining structural and functional properties of cytokines followed by a literature precedence‐based demonstration that Aβ possesses all 30 properties; this categorization of cytokine characteristics enabled an organized comparison of cytokines and Aβ, thereby providing systematic justification for classifying Aβ as a cytokine. The conclusion that Aβ is a cytokine enables the merger of two leading hypotheses of AD (amyloid hypothesis and neuroinflammation) into a single process.
Optimizing Electrocatalytic Nitrogen Reduction via Interfacial Electric Field Modulation: Elevating d‐Band Center in WS2‐WO3 for Enhanced Intermediate Adsorption
Authors: Wang Xiaoxuan , Li Shuyuan , Yuan Zhi , Sun Yanfei , Tang Zheng , Gao Xueying , Zhang Huiying , Li Jingxian , Wang Shiyu , Yang Dongchun , Xie Jiangzhou , Yang Zhiyu , Yan Yi‐Ming
Published: May 2023

Electrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, the protonation of intermediates is the rate‐determining step (RDS). Enhancing the adsorption of intermediates is crucial to increase the protonation of intermediates, which can lead to improved catalytic performance. Herein, we constructed a strong interfacial electric field in WS2‐WO3 to elevate the d‐band center of W, thereby strengthening the adsorption of intermediates. Experimental results demonstrated that this approach led to a significantly improved ENRR performance. Specifically, WS2‐WO3 exhibited a high NH3 yield of 62.38 μg h−1 mgcat−1 and a promoted faraday efficiency (FE) of 24.24 %. Furthermore, in situ characterizations and theoretical calculations showed that the strong interfacial electric field in WS2‐WO3 upshifted the d‐band center of W towards the Fermi level, leading to enhanced adsorption of −NH2 and −NH intermediates on the catalyst surface. This resulted in a significantly promoted reaction rate of the RDS. Overall, our study offers new insights into the relationship between interfacial electric field and d‐band center and provides a promising strategy to enhance the intermediates adsorption during the ENRR process.
Exploring the Strain Effect in Single Particle Electrochemistry using Pd Nanocrystals
Authors: Zhao Jiao , Wang Menglin , Peng Yu , Ni Jie , Hu Sunpei , Zeng Jie , Chen Qianjin
Published: May 2023

Tuning the surface strain of heterogeneous catalysts is recognized as a powerful strategy for tailoring their catalytic activity. However, a clear understanding of the strain effect in electrocatalysis at single‐particle resolution is still lacking. Here, we explore the electrochemical hydrogen evolution reaction (HER) of single Pd octahedra and icosahedra with the same surface bounded {111} crystal facet and similar sizes using scanning electrochemical cell microscopy (SECCM). It is revealed that tensilely strained Pd icosahedra display significantly superior HER electrocatalytic activity. The estimated turnover frequency at −0.87 V vs RHE on Pd icosahedra is about two times higher than that on Pd octahedra. Our single‐particle electrochemistry study using SECCM at Pd nanocrystals unambiguously highlights the importance of tensile strain on electrocatalytic activity and may offer new strategy for understanding the fundamental relationship between surface strain and reactivity.
A Cleavable Crosslinking Strategy for Commodity Polymer Functionalization and Generation of Reprocessable Thermosets
Authors: Bi Liting , Godwin Benjamin , Baran Miranda J. , Nazir Rashid , Wulff Jeremy E.
Published: May 2023

Covalently crosslinked polymeric materials, known as thermosets, possess enhanced mechanical strength and thermal stability relative to the corresponding uncrosslinked thermoplastics. However, the presence of covalent inter‐chain crosslinks that makes thermosets so attractive is precisely what makes them so difficult to reprocess and recycle. Here, we demonstrate the introduction of chemically cleavable groups into a bis‐diazirine crosslinker. Application of this cleavable crosslinker reagent to commercial low‐functionality polyolefins (or to a small‐molecule model) results in the rapid, efficient introduction of molecular crosslinks that can be uncoupled by specific chemical inputs. These proof‐of‐concept findings provide one potential strategy for circularization of the thermoplastic/thermoset plastics economy, and may allow crosslinked polyolefins to be manufactured, used, reprocessed, and re‐used without losing value. As an added benefit, the method allows the ready introduction of functionality into non‐functionalized commodity polymers.
Feinjustierung von Substrat–Katalysator Halogen–Halogen Interaktionen zur Steigerung der Enantioselektivität in der Halogenbrückenbindungs‐Katalyse
Authors: Keuper Alica C. , Fengler Kevin , Ostler Florian , Danelzik Tobias , Piekarski Dariusz G. , García Mancheño Olga
Published: May 2023

Ein neuer Ansatz für eine hoch enantioselektive Halogenbrückenbindungs‐Katalyse wurde entwickelt. Um die intrinsischen Probleme der Halogenbrückenbindungen (XB) und die daraus resultierenden ungelösten Limitierungen in der asymmetrischen Katalyse zu umgehen, wurden fein justierte Halogen–Halogen Interaktionen zwischen dem Substrat und dem XB‐Donor designt, um das Substrat im Katalysatorhohlraum vorzuorganisieren und die Kontrolle über die Enantioselektivität zu verbessern. Bei der vorliegenden Strategie wurden sowohl die Elektronenwolke (Lewis basische Stelle) als auch die sigma (σ)‐Loch Stelle des Halogen‐substituenten der Substrate genutzt, um einen engen chiralen Katalysator–Substrat–Gegenanion Komplex zu bilden. Dies ermöglicht eine kontrollierte Einführung eines hohen Chiralitätstransfers. Bemerkenswerte Enantioselektivitäten von bis zu 95 : 5 e.r. (90 %ee) wurden erreicht in einer Modell‐Dearomatisierungsreaktion von halogensubstituierten (Iso)chinolinen mit mehrzähnigen anionen‐bindenden Tetrakis‐Iodotriazol Katalysatoren.
Managing Multiple Halide‐Related Defects for Efficient and Stable Inorganic Perovskite Solar Cells
Authors: Wang Zhiteng , Tian Qingwen , Zhang Hao , Xie Huidong , Du Yachao , Liu Lei , Feng Xiaolong , Najar Adel , Ren Xiaodong , Liu Shengzhong (Frank)
Published: May 2023

Halide‐related surface defects on inorganic halide perovskite not only induce charge recombination but also severely limit the long‐term stability of perovskite solar cells. Herein, adopting density functional theory calculation, we verify that iodine interstitials (Ii) has a low formation energy similar to that of the iodine vacancy (VI) and is also readily formed on the surface of all‐inorganic perovskite, and it is regarded to function as an electron trap. We screen a specific 2,6‐diaminopyridine (2,6‐DAPy) passivator, which, with the aid of the combined effects from halogen‐Npyridine and coordination bonds, not only successfully eliminates the Ii and dissociative I2 but also passivates the abundant VI. Furthermore, the two symmetric neighboring ‐NH2 groups interact with adjacent halides of the octahedral cluster by forming hydrogen bonds, which further promotes the adsorption of 2,6‐DAPy molecules onto the perovskite surface. Such synergetic effects can significantly passivate harmful iodine‐related defects and undercoordinated Pb2+, prolong carrier lifetimes and facilitate the interfacial hole transfer. Consequently, these merits enhance the power‐conversion efficiency (PCE) from 19.6 % to 21.8 %, the highest value for this type of solar cells, just as importantly, the 2,6‐DAPy‐treated CsPbI3−xBrx films show better environmental stability.
Bi‐affinity Electrolyte Optimizing High‐Voltage Lithium‐Rich Manganese Oxide Battery via Interface Modulation Strategy
Authors: Yuan Xuedi , Dong Tao , Liu Jiaxin , Cui Yingyue , Dong Haotian , Yuan Du , Zhang Haitao
Published: May 2023

The practical implementation of high‐voltage lithium‐rich manganese oxide (LRMO) cathode is limited by the unanticipated electrolyte decomposition and dissolution of transition metal ions. The present study proposes a bi‐affinity electrolyte formulation, wherein the sulfonyl group of ethyl vinyl sulfone (EVS) imparts a highly adsorptive nature to LRMO, while fluoroethylene carbonate (FEC) exhibits a reductive nature towards Li metal. This interface modulation strategy involves the synergistic use of EVS and FEC as additives to form robust interphase layers on the electrode. As‐formed S‐endorsed but LiF‐assisted configuration cathode electrolyte interphase with a more dominant −SO2− component may promote the interface transport kinetics and prevent the dissolution of transition metal ions. Furthermore, the incorporation of S component into the solid electrolyte interphase and the reduction of its poorly conducting component can effectively inhibit the growth of lithium dendrites. Therefore, a 4.8 V LRMO/Li cell with optimized electrolyte may demonstrate a remarkable retention capacity of 97 % even after undergoing 300 cycles at 1 C.
Interface modified Si@SiO2/PVDF composite dielectrics with synchronously ameliorative dielectric and mechanical properties
Authors: Kong Fanrong , Zhou Wenying , Peng Weiwei , Liang Chen , Wu Hongju , Lin Na , Wang Guangheng , Liu Dengfeng , Feng Aihong , Liu Xiangrong
Published: May 2023

To efficaciously decrease dielectric loss while still synchronously harvesting a high dielectric constant (ε′) and breakdown strength (Eb), as well as good mechanical properties in silicon (Si)/poly(vinylidene fluoride) (PVDF), in this work, the core@shell structured Si@silicon dioxide (SiO2) particles were first prepared via a high temperature oxidation, and subsequently incorporated into the PVDF to generate morphology‐dependent composites with a high‐ε′ and Eb but low loss. The SiO2 shell effects on the morphology, dielectric, and mechanical properties of PVDF composites were explored. In comparison to pristine Si/PVDF, the Si@SiO2/PVDF presents significantly suppressed loss and boosted Eb because the SiO2 interlayer not only efficiently blocks the connection between the raw Si and greatly impedes the long‐range charges migration even at high filler loadings, but also obviously improves the compatibility between Si and PVDF at the interfaces which promotes fillers' uniform dispersion in host matrix, thus leading to enhanced dielectric and mechanical properties. The fitting result by the Havriliak–Negami equation theoretically elucidates the SiO2 interlayer's suppression effect on charge migration behavior in the composites. More importantly, dielectric properties can be efficiently turned via tailoring the SiO2 shell thickness. The Si@SiO2/PVDF with simultaneously enhanced dielectric and mechanical performances shows promising uses in the electrical and microelectronics industries.
Effect of electron beam irradiation on thermal stability and crystallization behavior of flexible copolyester/multiwalled carbon nanotubes nanocomposites
Authors: Dhakal Kedar Nath , Lach Ralf , Grellmann Wolfgang , Müller Michael Thomas , Krause Beate , Pionteck Jürgen , Adhikari Rameshwar
Published: May 2023

Poly(butylene adipate‐co‐terephthalate) (PBAT), a biodegradable copolyester, was used as the polymer matrix to prepare nanocomposites with multiwalled carbon nanotubes (MWCNT) by melt‐mixing followed by hot‐pressing. The PBAT/MWCNT nanocomposites were exposed to electron beam (EB) irradiation, and thermal stability, melting and crystallization behavior of irradiated and unirradiated nanocomposites were comparatively investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. TGA results reveal increased thermal stability (up to 17°C) and maximum degradation temperature (Tmax) (up to 15°C) of PBAT/MWCNT nanocomposites, attributed to the high thermal stability of MWCNT and good MWCNT–PBAT interfacial interactions. However, the activation energy for thermal degradation (Ea) decreased with the presence of MWCNT in comparison to neat PBAT regardless of the MWCNT concentration. Both the thermal stability and Tmax of irradiated nanocomposites decreased by 3°C despite the crosslinking which can be attributed to successive minor irradiation‐induced polymer degradation, while Ea remained unchanged. Declined melting temperature (Tm), enthalpy of crystallization, enthalpy of melting and crystallinity of nanocomposites with the presence of MWCNT suggest the formation of less perfect crystals. Meanwhile, their increased glass transition temperature (Tg) and crystallization temperature (Tc) are due to the increased rigidity of PBAT chains and a reduced crystallization process in the presence of MWCNT, respectively. Similarly, reduced crystallinity and values of Tm and Tc of EB‐irradiated nanocomposites by 4.1%, 9.6%, and 7.5%, respectively, signifying the presence of PBAT‐crosslinks resulting in crystal defects.
Near‐Field Nano‐Optical Imaging of van der Waals Materials
Authors: Kwon Soyeong , Kim Jin Myung , Ma Peiwen J. , Guan Weilin , Nam SungWoo
Published: May 2023

2D van der Waals (vdW) materials are emerging as the next generation platform for optical and electronic devices with their wide coverage of the energy bandgaps. The strong light–matter interactions in 2D vdW layers allow for exploring novel optical and electronic phenomena such as 2D polaritons exhibiting ultrahigh field confinement, defects‐induced new quantum states, and strain‐modulated quantum confinement of 2D excitons. Far‐field optical imaging techniques are extensively used to characterize the 2D vdW materials so far, however, subdiffraction spatial resolution is required for comprehensive investigations of 2D vdW materials of which physical properties are greatly influenced by local defects and strain. This article aims to cover historical advances, fundamental principles, and distinct features of emerging near‐field optical imaging techniques: scattering‐type scanning near‐field optical microscopy, tip‐enhanced Raman spectroscopy, tip‐enhanced photoluminescence techniques, and photo‐induced force microscopy. The recent developments toward spectroscopic analysis of near‐field imaging and applications for unveiling unique properties of 2D polaritons, nanoscale defects, and mechanical strains in 2D vdW materials, are also discussed. This review article provides an understanding of emerging near‐field imaging techniques and suggests prospective applications for exploring 2D vdW materials.
Thinking inside the box: An evaluation of a novel search‐assisting tool for supporting (meta)cognition during exploratory search
Authors: Li Yuan , Crescenzi Anita , Ward Austin R. , Capra Rob
Published: May 2023

Exploratory searches involve significant cognitively demanding aiming at learning and investigation. However, users gain little support from search engines for their cognitive and metacognitive activities (e.g., discovery, synthesis, planning, transformation, monitoring, and reflection) during exploratory searches. To better support the exploratory search process, we designed a new search assistance tool called OrgBox. OrgBox allows users to drag‐and‐drop information they find during searches into “boxes” and “items” that can be created, labeled, and rearranged on a canvas. We conducted a controlled, within‐subjects user study with 24 participants to evaluate the OrgBox versus a baseline tool called the OrgDoc that supported rich‐text features. Our findings show that participants perceived the OrgBox tool to provide more support for grouping and reorganizing information, tracking thought processes, planning and monitoring search and task processes, and gaining a visual overview of the collected information. The usability test reveals users' preferences for simplicity, familiarity, and flexibility of the design of OrgBox, along with technical problems such as delay of response and restrictions of use. Our results have implications for the design of search‐assisting systems that encourage cognitive and metacognitive activities during exploratory search processes.
Distributed dynamic matrix control with constrained optimization for collision and obstacle avoidance of simulated multiple quadcopters
Authors: Dubay Shaundell , Pan Ya‐Jun
Published: May 2023

A system of fast moving quadcopters has a high risk of collisions with neighboring quadcopters or obstacles. The objective of this work is to develop a control strategy for collision and obstacle avoidance of multiple quadcopters. In this paper, the problem of distributed dynamic matrix control (DMC) for collision avoidance among a team of multiple quadcopters attempting to reach consensus in the horizontal plane and yaw direction ( , and ) is investigated. Violations of a predetermined safety radius generates output constraints on the DMC optimization function, which has not been dealt with in the literature. Different from past works, the proposed strategy can perform collision avoidance in the , , and ‐directions. In addition, logarithmic barrier functions are implemented as input rate constraints on the control actions. Extensive simulation studies for a team of quadcopters illustrate promising results of the proposed control strategy and case variations. In addition, DMC parameter effects on the system performance are studied, and a successful study for obstacle avoidance is presented.
Stachydrine, N‐acetylornithine and trimethylamine N‐oxide levels as candidate milk biomarkers of maternal consumption of an obesogenic diet during lactation
Authors: Castillo Pedro , Kuda Ondrej , Kopecky Jan , Pomar Catalina Amadora , Palou Andreu , Palou Mariona , Picó Catalina
Published: May 2023

We aimed to evaluate whether improving maternal diet during lactation in diet‐induced obese rats reverts the impact of western diet (WD) consumption on the metabolome of milk and offspring plasma, as well as to identify potential biomarkers of these conditions. Three groups of dams were followed: control‐dams (CON‐dams), fed with standard diet (SD); WD‐dams, fed with WD prior and during gestation and lactation; and reversion‐dams (REV‐dams), fed as WD‐dams but moved to SD during lactation. Metabolomic analysis was performed in milk at lactation days 5, 10, and 15, and in plasma from their male and female offspring at postnatal day 15. Milk of WD‐dams presented, throughout lactation and compared to CON‐dams, altered profiles of amino acids and of the carnitine pool, accompanied by changes in other polar metabolites, being stachydrine, N‐acetylornithine, and trimethylamine N‐oxide the most relevant and discriminatory metabolites between groups. The plasma metabolome profile was also altered in the offspring of WD‐dams in a sex‐dependent manner, and stachydrine, ergothioneine and the acylcarnitine C12:1 appeared as the top three most discriminating metabolites in both sexes. Metabolomic changes were largely normalized to control levels both in the milk of REV‐dams and in the plasma of their offspring. We have identified a set of polar metabolites in maternal milk and in the plasma of the offspring whose alterations may indicate maternal intake of an unbalanced diet during gestation and lactation. Levels of these metabolites may also reflect the beneficial effects of implementing a healthier diet during lactation.
Development of an aminotransferase‐driven biocatalytic cascade for deracemization of d,l‐phosphinothricin
Authors: Liu Han‐Lin , Wu Jia‐Min , Deng Xin‐Tong , Yu Lan , Yi Pu‐Hong , Liu Zhi‐Qiang , Xue Ya‐Ping , Jin Li‐Qun , Zheng Yu‐Guo
Published: May 2023

2‐oxo‐4‐[(hydroxy)(methyl)phosphinoyl]butyric acid (PPO) is the essential precursor keto acid for the asymmetric biosynthesis of herbicide l‐phosphinothricin (l‐PPT). Developing a biocatalytic cascade for PPO production with high efficiency and low cost is highly desired. Herein, a d‐amino acid aminotransferase from Bacillus sp. YM‐1 (Ym DAAT) with high activity (48.95 U/mg) and affinity (Km = 27.49 mM) toward d‐PPT was evaluated. To circumvent the inhibition of by‐product d‐glutamate (d‐Glu), an amino acceptor (α‐ketoglutarate) regeneration cascade was constructed as a recombinant Escherichia coli (E. coli D), by coupling Ym d‐AAT, d‐aspartate oxidase from Thermomyces dupontii (TdDDO) and catalase from Geobacillus sp. CHB1. Moreover, the regulation of the ribosome binding site was employed to overcome the limiting step of expression toxic protein TdDDO in E. coli BL21(DE3). The aminotransferase‐driven whole‐cell biocatalytic cascade (E. coli D) showed superior catalytic efficiency for the synthesis of PPO from d,l‐phosphinothricin (d,l‐PPT). It revealed the production of PPO exhibited high space–time yield (2.59 g L−1 h−1) with complete conversion of d‐PPT to PPO at high substrate concentration (600 mM d,l‐PPT) in 1.5 L reaction system. This study first provides the synthesis of PPO from d,l‐PPT employing an aminotransferase‐driven biocatalytic cascade.
Photochemical Synthesis of Covalent Organic Frameworks
Authors: Wu Cheng‐Juan , Shao Ming‐Zhen , Geng Yan , Dong Yu‐Bin
Published: May 2023

As a booming class of crystalline porous materials, covalent organic frameworks (COFs) have attracted increasing attention and various methods to construct COFs have been investigated including solvothermal synthesis, ionothermal synthesis, microwave synthesis, mechanical synthesis, sonochemical synthesis, interfacial synthesis, and electrochemical synthesis. Recently, photochemical reaction has emerged as a powerful approach for COF synthesis, which utilizing the non‐toxic, abundant and renewable light as the energy source. Benefitting from its outstanding properties of low‐cost, safety, and environmental friendliness, the photochemical reaction was considered as a promising alternative to the conventional thermal reaction for COF synthesis. In this concept article, we summarized the up‐to‐date reports about the photochemical synthesis of COFs and provided a future perspective in this field. It is anticipated that this concept could be beneficial for the further development of photochemical synthesis of COFs.
A Predictive Model for the Pd‐Catalyzed Site‐Selective Oxidation of Diols
Authors: Marinus Nittert , Eisink Niek N. H. M. , Reintjens Niels R. M. , Dijkstra Renger S. , Havenith Remco W. A. , Minnaard Adriaan J. , Witte Martin D.
Published: May 2023

A predictive model, shaped as a set of rules, is presented that predicts site‐selectivity in the mono‐oxidation of diols by palladium‐neocuproine catalysis. For this, the factors that govern this site‐selectivity within diols and between different diols have been studied both experimentally and with computation. It is shown that an electronegative substituent antiperiplanar to the C−H bond retards hydride abstraction, resulting in a lower reactivity. This explains the selective oxidation of axial hydroxy groups in vicinal cis‐diols. Furthermore, DFT calculations and competition experiments show how the reaction rate of different diols is determined by their configuration and conformational freedom. The model has been validated by the oxidation of several complex natural products, including two steroids. From a synthesis perspective, the model predicts whether a natural product comprising multiple hydroxy groups is a suitable substrate for site‐selective palladium‐catalyzed oxidation.
Design of molecularly imprinted resin material with sulfonic acid functionalization for enantioseparation of (±)‐cathine
Authors: Alhawiti Aliyah S.
Published: May 2023

In the current work, an enantioselective imprinting technique was used to develop a very selective adsorbent for the (+)‐cathine ((+)‐Cat) enantiomer. The phenolic sulfonamide produced from 2,4‐dihydroxybenzenesulfonic acid (HBS) and (+)‐Cat ((+)‐Cat‐HBS) was initially synthesized by triphenylphosphene activation and subsequently involved in condensation polymerization with resorcinol in the presence of formaldehyde under acidic conditions. Alkaline sulfonamide bond‐breaking was subsequently employed to separate the (+)‐Cat template from the polymer, and the resulting imprinted resin ((+)‐CIP) displayed high selectivity for the (+)‐Cat, with a capacity of 225 ± 2 mg/g. Studies of selectivity also showed that the (+)‐Cat enantiomer was preferred over its counterpart because of the development of configurationally matching receptors. In addition, the produced resin was used for the enantioresolution of (±)‐Cat racemate by column method, yielding a loading supernatant solution with an enantiomeric excess of (+)‐Cat 50% and a recovery eluant solution with an excess of (−)‐Cat 85%.
Performance assessment of drop tube reactor for biomass fast pyrolysis using process simulator
Authors: Wako Fekadu Mosisa , Pio Gianmaria , Lofti Ashraf , Salzano Ernesto , Farooqui Azharuddin , Mahinpey Nader
Published: May 2023

Biomass pyrolysis process from a drop tube reactor was modelled in a plug flow reactor using Aspen Plus process simulation software. A kinetic mechanism for pyrolysis was developed considering the recent improvements and updated kinetic schemes to account for different content of cellulose, hemicellulose, and lignin. In this regard, oak, beechwood, rice straw, and cassava stalk biomasses were analyzed. The main phenomena governing the pyrolysis process are identified in terms of the characteristic times. Pyrolysis process was found to be reaction rate controlled. Effects of pyrolysis temperature on bio‐oil, gases, and char yields were evaluated. At optimum pyrolysis conditions (i.e., 500°C), a bio‐oil yield of 67.3, 64, 43, and 52 wt.% were obtained from oak, beechwood, rice straw, and cassava stalk, respectively. Oak and beechwood were found to give high yields of bio‐oil, while rice straw produced high gas and char yields compared to other biomasses. Although temperature is the main factor that plays a key role in the distribution of pyrolysis products, the composition of cellulose, hemicellulose, and lignin in the feedstock also determines the yield behaviour and composition of products. With the rise in pyrolysis temperature, further decomposition of intermediate components was initiated favouring the formation of lighter fractions. Comparably, species belonging to the aldehyde chemical family had the highest share of bio‐oil components in all the investigated feedstocks. Overall, the present study shows a good agreement with the experimental study reported in the literature, confirming its validity as a predictive tool for the biomass pyrolysis process.
Electronic Structure, Aromaticity and Optical Properties of Dehydro[10]annulene
Authors: Gai Xinwen , Zhang Lei , Wang Jingang
Published: May 2023

Dehydro[10]annulene had been prepared experimentally recently, which is considered to be a highly rigid structure with planar configuration. In this paper, the electronic structure and bonding character of dehydro[10]annulene had been studied by means of molecular orbital (MO), density of states (DOS), bond order (BO) and interaction region indicator (IRI) analyses. The delocalization characters of out‐of‐plane and in‐plane π‐electrons (πout‐ and πin‐electrons) of the bond regions were studied by using localized orbital locator (LOL). The anisotropy of the induced current density (AICD), iso‐chemical shielding surface (ICSS) and anisotropy of the gauge‐including magnetically induced current (GIMIC) were used to investigate the molecular response to external magnetic field, including the induced ring current and the magnetic shielding characteristic. The results showed that the electron delocalization of dehydro[10]annulene is mainly contributed by πout system. The apparent clockwise current in the πout system proved that dehydro[10]annulene is πout aromatic. Finally, the photophysical properties and (hyper)polarizability of dehydro[10]annulene were studied by TD‐DFT calculation. The results showed that dehydro[10]annulene has strong local excitation characters. Its (hyper)polarizability decreases with the increase of frequency and has the characteristics of nonlinear anisotropy.
Construction of a 21‐Membered‐Ring Orifice on [60]Fullerene
Authors: Hashikawa Yoshifumi , Sadai Shumpei , Murata Yasujiro
Published: May 2023

Open‐[60]fullerenes possessing a huge orifice with a ring‐atom count exceeding 19 have been confined to only a few examples. Herein, we report a 20‐membered‐ring orifice which enables for a guest molecule such as H2, N2, and CH3OH to be encapsulated inside the [60]fullerene cavity. In addition, a 21‐membered‐ring orifice was prepared via a reductive decarbonylation, in which one of the carbon atoms was moved out of the [60]fullerene skeleton as an N,N‐dimethylamide group. At a low temperature of −30 °C, an Ar atom was encapsulated with an occupation level up to 52 %. At around room temperature, the amide group on the orifice rotates along with the C(amide)−C(fullerene) bond axis, realizing a self‐inclusion of the methyl substituent on the amide group as confirmed NMR spectroscopically and computationally.
Productivity variation and stability of intensive forage‐winter wheat cropping systems on the Loess Plateau, China
Authors: Lai Xingfa , Guan Tongtong , Dong Xiu , Jia Xueyi , Shen Yuying
Published: May 2023

Integrating forage crops into the continuous winter wheat (Triticum aestivum L.) cropping system can be used for increasing rural population income and maintaining grain production on the Loess Plateau. The objective of this study was to comprehensively evaluate economic yield (EYyield), dry matter yield (DMyield), crude protein yield (CPyield), wheat equivalent yield (WEyield), and food equivalent yield (FEUyield) when incorporating annual forages (oat [Avena sativa L.], soybean [Glycine max L.], and vetch [Vicia sativa L.]) into the traditional fallow‐winter wheat system from a 4‐year (2016–2020) experiment on the Loess Plateau of China. Results showed that incorporating annual forages into the continuous wheat system significantly increased system productivity. Among the four growing seasons, average system DMyield values for fallow‐winter wheat (F‐W), oat‐winter wheat (O‐W), soybean‐winter wheat (S‐W), and vetch‐winter wheat (V‐W) were 10348.52, 13854.15, 14679.94, and 12185.29 kg ha−1, respectively. The average wheat EYyield values were 3777.82, 3115.19, 4020.76, and 3180.71 kg ha−1, respectively. The average forage DMyield values were 0.00, 5497.19, 4284.64, and 2817.50 kg ha−1, respectively. The S‐W system had the highest DMyield and CPyield (1350.10 kg ha−1), and also had DMyield with the smallest variation (CV = 15.21%). The O‐W, S‐W, and V‐W systems produced FEUyield values that were 48.67%, 68.46%, and 30.53%, respectively, greater than the F‐W system. When considering market prices and yields, the S‐W system increased wheat gain yield and had the highest WEyield (6607.90 kg ha−1). Therefore, in consideration of forage quality, winter wheat production, and system productivity, we recommend the S‐W system for local farmers on the Loess Plateau.
Guidelines on offloading foot ulcers in persons with diabetes (IWGDF 2023 update)
Authors: Bus Sicco A. , Armstrong David G. , Crews Ryan T. , Gooday Catherine , Jarl Gustav , Kirketerp‐Moller Klaus , Viswanathan Vijay , Lazzarini Peter A.
Published: May 2023

Aims

Offloading mechanical tissue stress is arguably the most important of multiple interventions needed to heal diabetes‐related foot ulcers. This is the 2023 International Working Group on the Diabetic Foot (IWGDF) evidence‐based guideline on offloading interventions to promote healing of foot ulcers in persons with diabetes. It serves as an update of the 2019 IWGDF guideline.

Materials and Methods

We followed the GRADE approach by devising clinical questions and important outcomes in the PICO (Patient‐Intervention‐Control‐Outcome) format, undertaking a systematic review and meta‐analyses, developing summary of judgement tables and writing recommendations and rationales for each question. Each recommendation is based on the evidence found in the systematic review, expert opinion where evidence was not available, and a careful weighing of GRADE summary of judgement items including desirable and undesirable effects, certainty of evidence, patient values, resources required, cost effectiveness, equity, feasibility, and acceptability.

Results

For healing a neuropathic plantar forefoot or midfoot ulcer in a person with diabetes, use a non‐removable knee‐high offloading device as the first‐choice offloading intervention. If contraindications or patient intolerance to non‐removable offloading exist, consider using a removable knee‐high or ankle‐high offloading device as the second‐choice offloading intervention. If no offloading devices are available, consider using appropriately fitting footwear combined with felted foam as the third‐choice offloading intervention. If such a non‐surgical offloading treatment fails to heal a plantar forefoot ulcer, consider an Achilles tendon lengthening, metatarsal head resection, joint arthroplasty, or metatarsal osteotomy. For healing a neuropathic plantar or apex lesser digit ulcer secondary to flexibile toe deformity, use digital flexor tendon tenotomy. For healing rearfoot, non‐plantar or ulcers complicated with infection or ischaemia, further recommendations have been outlined. All recommendations have been summarised in an offloading clinical pathway to help facilitate the implementation of this guideline into clinical practice.

Conclusion

These offloading guideline recommendations should help healthcare professionals provide the best care and outcomes for persons with diabetes‐related foot ulcers and reduce the person's risk of infection, hospitalisation and amputation.
β‐Catenin in the kidney stroma modulates pathways and genes to regulate kidney development
Authors: Deacon Erin , Li Anna , Boivin Felix , Dvorkin‐Gheva Anna , Cunanan Joanna , Bridgewater Darren
Published: May 2023

Background

Kidney development is regulated by cellular interactions between the ureteric epithelium, mesenchyme, and stroma. Previous studies demonstrate essential roles for stromal β‐catenin in kidney development. However, how stromal β‐catenin regulates kidney development is not known. We hypothesize that stromal β‐catenin modulates pathways and genes that facilitate communications with neighboring cell populations to regulate kidney development.

Results

We isolated purified stromal cells with wild type, deficient, and overexpressed β‐catenin by fluorescence‐activated cell sorting and conducted RNA Sequencing. A Gene Ontology network analysis demonstrated that stromal β‐catenin modulates key kidney developmental processes, including branching morphogenesis, nephrogenesis and vascular formation. Specific stromal β‐catenin candidate target genes that may mediate these effects included secreted, cell‐surface and transcriptional factors that regulate branching morphogenesis and nephrogenesis (Wnts, Bmp, Fgfr, Tcf/Lef) and secreted vascular guidance cues (Angpt1, VEGF, Sema3a). We validated established β‐catenin targets including Lef1 and novel candidate β‐catenin targets including Sema3e which have unknown roles in kidney development.

Conclusions

These studies advance our understanding of gene and biological pathway dysregulation in the context of stromal β‐catenin misexpression during kidney development. Our findings suggest that during normal kidney development, stromal β‐catenin may regulate secreted and cell‐surface proteins to communicate with adjacent cell populations.
A values‐engaged, educative training model for novice evaluators
Authors: Reid Aileen M. , Boyce Ayesha S. , Chuquiruna Joy Alcantara , Somo‐Aina Omodolapo , Malloy Caraline , Stephenson Sara
Published: May 2023

The next generation of evaluators must be trained and mentored in high‐quality technical, strengths‐based, interpersonal, contextual, social justice‐oriented, and values‐engaged evaluation. In this chapter, we present a non‐course‐based, real‐world‐focused, adaptable training model for anyone working with novice evaluators. In creating this model, we have drawn from our multiple identities—educator, faculty, graduate student, first‐generation, woman, Black, Latina, white, United States Citizen, immigrant, wife, mother, advocate, and change agent—and from our experiences, previous research on evaluation, culturally responsive evaluation approaches, higher education literature, and personal reflections. We outline our values‐engaged, educative training model and discuss its three key components. We conclude with thoughts about what evaluator education could and should become.
Individualized targeting is warranted in subcallosal cingulate gyrus deep brain stimulation for treatment‐resistant depression: A tractography analysis
Authors: Zhu Zhoule , Han Jiawei , Zhu He , Cai Chengwei , Feng Chen , Guo Xinxia , Ying Yuqi , Jiang Hongjie , Zheng Zhe , Zhang Jianmin , Zhu Junming , Wu Hemmings
Published: May 2023

Subcallosal cingulate gyrus (SCG) is a target of deep brain stimulation (DBS) for treatment‐resistant depression. However, previous randomized controlled trials report that approximately 42% of patients are responders to this therapy of last resort, and suboptimal targeting of SCG is a potential underlying factor to this unsatisfactory efficacy. Tractography has been proposed as a supplementary method to enhance targeting strategy. We performed a connectivity‐based segmentation in the SCG region via probabilistic tractography in 100 healthy volunteers from the Human Connectome Project. The SCG voxels with maximum connectivity to brain regions implicated in depression, including Brodmann Area 10 (BA10), cingulate cortex, thalamus, and nucleus accumbens were identified, and the conjunctions were deemed as tractography‐based targets. We then performed deterministic tractography using these targets in additional 100 volunteers to calculate streamline counts compassing to relevant brain regions and fibers. We also evaluated the intra‐ and inter‐subject variance using test–retest dataset. Two tractography‐based targets were identified. Tractography‐based target‐1 had the highest streamline counts to right BA10 and bilateral cingulate cortex, while tractography‐based target‐2 had the highest streamline counts to bilateral nucleus accumbens and uncinate fasciculus. The mean linear distance from individual tractography‐based target to anatomy‐based target was 3.2 ± 1.8 mm and 2.5 ± 1.4 mm in left and right hemispheres. The mean ± SD of targets between intra‐ and inter‐subjects were 2.2 ± 1.2 and 2.9 ± 1.4 in left hemisphere, and 2.3 ± 1.4 and 3.1 ± 1.7 in right hemisphere, respectively. Individual heterogeneity as well as inherent variability from diffusion imaging should be taken into account during SCG‐DBS target planning procedure.
Bringing a Mechanistic Lens to the Development of New Transfer Hydroarylation Isodesmic Reactions for the Synthesis of Amides, Thioamides, Amidines, Alkenes and Ketones from Carboxylic Acids via Extrusion and Insertion Elementary Steps
Authors: O'Hair Richard A. J.
Published: May 2023

The wide availability, ease of handling and structural and functional diversity make carboxylic acids prized building blocks in organic synthesis. The past two decades has seen an explosion of interest in the development of new modes of reactivity of carboxylic acids and their derivatives. Of these, metal‐mediated decarboxylation reactions are attractive as they produce organometallic intermediates that can subsequently be used in C−X (where X=C, N, S etc) bond coupling reactions. Here the results of mechanistic studies integrating both gas‐ and condensed‐phase work are described for development of new extrusion‐insertion (ExIn) classes of reactions for the synthesis of amides, thioamides, amidines, alkenes and ketones from arylcarboxylic acids and suitable (hetero)cumulenes.
Open doors: The impact of border reforming and opening policies on the regional border economies of China
Authors: Zhang Xiekui , Zuo Xinfeng , Chen Xinjian
Published: May 2023

The openness and security of a country's borders is a matter of concern for countries worldwide. Since its reform and opening up in 1978, China has implemented reforming and opening policies in border regions, as represented by the “Xingbian Fumin Xingdong” (Revitalize Border Areas and Enrich Residents' Lives Policy [RBAERL Policy]) to achieve economic prosperity and stability. This study evaluated the impacts of the RBAERL policy in terms of outcomes related to county‐level economic growth in China's border regions. Using China's county‐level panel data from 1999 to 2016, we applied a spatial discontinuity design with the geographical boundary serving as the running variable. We found that the RBAERL policy contributed significantly to the economic growth of the border counties. These results were shown to be robust when measured against a series of test procedures. Through a by‐segment analysis of the border regions, we found that the policy had the strongest effect in northeastern China. Further mechanism analysis showed that the effect of per capita GDP growth primarily resulted from the expansion of the industrial sector along with physical and human capital investment rather than the promotion of employment and the growth of total factor productivity. The findings of this study can provide references for the importance of open borders for economic development and national security.
PtZn@CN/CC derived from ZIF–86 for high‐performance hydrogen evolution in acid and alkaline electrolyte
Authors: Wang Yajie , Lu Shuangqiang , Wang Yi , Wang Bin , Liu Zhongqing
Published: May 2023

Background

The high cost and scarcity of Pt metal limit the large‐scale applicability of the excellent hydrogen evolution reaction (HER) catalyst.

Objective

The current study aims to generate high‐performance HER electrodes with low Pt content.

Methods

Nitrogen‐doped carbon support has been produced via hydrothermal and calcination treatments of ZIF‐8 precursor. By applying drop coating, a CN/CC electrode support is fabricated before it is further decorated with Pt nanoparticles to afford a PtZn@CN/CC composite electrode through a cyclic voltammetry (CV) method.

Results

In 0.5 M H2SO4 at room temperature, the electrode achieves an HER overpotential of 74 mV at a current density of 10 mA cm–2. When the electrolyte is 1 M KOH, the electrode functions even more favorably with an overpotential of 55 mV under the same experimental conditions. The HER performance increases with a gain in temperature. At 80°C, alkaline overpotential of the electrode becomes 29 mV, much superior to the 20% Pt/C/CC electrode.

Conclusion

The study paves the method of feasibly constructing a high‐performance HER electrode with low Pt content. This composite electrode imparts synergistic effects between PtZn nanoparticles and CN support that enhance the electrochemically active surface area while reducing the reaction impedance to provide outstanding hydrogen evolution performance.
Self‐dual association schemes, fusions of Hamming schemes, and partial geometric designs
Authors: Xu Bangteng
Published: May 2023

Partial geometric designs can be constructed from basic relations of association schemes. An infinite family of partial geometric designs were constructed from the fusion schemes of certain Hamming schemes in work by Nowak et al. (2016). A general method to create partial geometric designs from association schemes is given by Xu (2023). In this paper, we continue the research by Xu (2023). We will first study the properties and characterizations of self‐dual association schemes. Then using the characterizations of self‐dual association schemes and the representation theory (character tables) of commutative association schemes, we obtain characterizations and classifications of self‐dual (symmetric or nonsymmetric) association schemes of rank 4 that produce as many as possible nontrivial partial geometric designs or 2‐designs. In particular, for a primitive self‐dual symmetric association scheme of rank 4, if is a power of 3 and each of , , and induces a partial geometric design, then we will prove that is algebraically isomorphic to a fusion scheme of the Hamming scheme for some odd number .