bluuebunny/crossref_metadata_2025 huggingface dataset:
Implanting CoOx Clusters on Ordered Macroporous ZnO Nanoreactors for Efficient CO2 Photoreduction
Authors: Wang Yan , Fan Guilan , Wang Sibo , Li Yunxiang , Guo Yan , Luan Deyan , Gu Xiaojun , Lou Xiong Wen (David)
Published: September 2022

Despite suffering from slow charge‐carrier mobility, photocatalysis is still an attractive and promising technology toward producing green fuels from solar energy. An effective approach is to design and fabricate advanced architectural materials as photocatalysts to enhance the performance of semiconductor‐based photocatalytic systems. Herein, metal–organic‐framework‐derived hierarchically ordered porous nitrogen and carbon co‐doped ZnO (N‐C‐ZnO) structures are developed as nanoreactors with decorated CoOx nanoclusters for CO2‐to‐CO conversion driven by visible light. Introduction of hierarchical nanoarchitectures with highly ordered interconnected meso–macroporous channels shows beneficial properties for photocatalytic reduction reactions, including enhanced mobility of charge carriers throughout the highly accessible framework, maximized exposure of active sites, and inhibited recombination of photoinduced charge carriers. Density functional theory calculations further reveal the key role of CoOx nanoclusters with high affinity to CO2 molecules, and the CoO bonds formed on the surface of the composite exhibit stronger charge redistribution. As a result, the obtained CoOx/N‐C‐ZnO demonstrates enhanced photocatalysis performance in terms of high CO yield and long‐term stability.
Doping Engineering in the MoS2/SnSe2 Heterostructure toward High‐Rejection‐Ratio Solar‐Blind UV Photodetection
Authors: Yu Yali , Shen Tao , Long Haoran , Zhong Mianzeng , Xin Kaiyao , Zhou Ziqi , Wang Xiaoyu , Liu Yue‐Yang , Wakabayashi Hitoshi , Liu Liyuan , Yang Juehan , Wei Zhongming , Deng Hui‐Xiong
Published: September 2022

The intentionally designed band alignment of heterostructures and doping engineering are keys to implement device structure design and device performance optimization. According to the theoretical prediction of several typical materials among the transition metal dichalcogenides (TMDs) and group‐IV metal chalcogenides, MoS2 and SnSe2 present the largest staggered band offset. The large band offset is conducive to the separation of photogenerated carriers, thus MoS2/SnSe2 is a theoretically ideal candidate for fabricating photodetector, which is also verified in the experiment. Furthermore, in order to extend the photoresponse spectrum to solar‐blind ultraviolet (SBUV), doping engineering is adopted to form an additional electron state, which provides an extra carrier transition channel. In this work, pure MoS2/SnSe2 and doped MoS2/SnSe2 heterostructures are both fabricated. In terms of the photoelectric performance evaluation, the rejection ratio R254/R532 of the photodetector based on doped MoS2/SnSe2 is five orders of magnitude higher than that of pure MoS2/SnSe2, while the response time is obviously optimized by 3 orders. The results demonstrate that the combination of band alignment and doping engineering provides a new pathway for constructing SBUV photodetectors.
Conditional Generative Adversarial Networks for Inverse Design of Multifunctional Metasurfaces
Authors: Kiani Mehdi , Kiani Jalal , Zolfaghari Mahsa
Published: September 2022

Electromagnetic (EM) metasurfaces can present a versatile platform for realization of multiple diverse EM functionalities with incident wave frequency, polarization, or propagation direction through appropriate choice of unit cells structures. However, the inverse design of multifunctional metasurfaces relies on massive full‐wave EM numerical simulations to obtain an optimized solution. Herein, a step‐by‐step procedure based on conditional generative adversarial networks (cGANs) integrated with Gramian angular fields (GAFs) to reduce the computational time required for the EM simulations in the inverse design of multifunctional microwave metasurfaces is proposed. The proposed procedure initially implements GAFs to encode the desired multiobjective scattering parameters (SPs) to images and then passes them through the cGAN model to map them to three‐layer metasurfaces. The present study uses a robust dataset, including 54 000 metasurface structures and corresponding SPs to train and validate the cGAN model. This article also presents two case study examples using two multifunctional metasurfaces with different independent functionalities and full‐space coverage to justify the performance of the proposed procedure in the inverse design of multifunctional microwave metasurfaces. The case studies demonstrate that, despite the random nature of the training data samples, the cGAN reliably predicts the corresponding metasurfaces of the desired multiobjective SPs.
Switchable Synthesis of Aldehydes and Carboxylic Acids from Alcohols by Platinum‐Catalysed Hydrogen Peroxide Oxidation Using Flow Reactors
Authors: Kon Yoshihiro , Nakashima Takuya , Onozawa Shun‐ya , Sato Kazuhiko , Kobayashi Shū
Published: September 2022

Switchable synthesis of aldehydes and carboxylic acids from alcohols by Pt‐catalysed H2O2 oxidation is performed for the first time using flow reactors. The use of an optimised amount of zero‐valent Pt black diluted with SiO2 catalyst demonstrates controlled H2O2 oxidation of allylic alcohols, benzyl alcohols, and aliphatic alcohols. From a probe reaction, Pt catalytic activity to produce a carboxylic acid from the corresponding alcohol improves depending on the temperature increasing from 40 to 90 °C. The set of reaction conditions about the combination of temperature and flow rate as a simple trigger works sensitively to divide the formation of aldehydes and carboxylic acids without tuning by additives.

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Photoresponsive Hydrogel‐Coated Upconversion Cyanobacteria Nanocapsules for Myocardial Infarction Prevention and Treatment
Authors: Liu Yu , Zhong Da , He Yizhe , Jiang Junkai , Xie Weichang , Tang Zhibo , Qiu Jianbin , Luo Jun , Wang Xiaolei
Published: September 2022

Myocardial infarction (MI) is a common disease that seriously threatens human health. It is noteworthy that oxygen is one of the key factors in the regulation of MI pathology procession: the controllable hypoxic microenvironment can enhance the tolerance of cardiac myocytes (CMs) and oxygen therapy regulates the immune microenvironment to repair the myocardial injury. Thus, the development of an oxygen‐controllable treatment is critically important to unify MI prevention and timely treatment. Here, a hydrogel encapsulated upconversion cyanobacterium nanocapsule for both MI prevention and treatment is successfully synthesized. The engineered cyanobacteria can consume oxygen via respiration to generate a hypoxic microenvironment, resulting in the upregulation of heat shock protein70 (HSP70), which can enhance the tolerance of CMs for MI. When necessary, under 980 nm near‐infrared (NIR) irradiation, the system releases photosynthetic oxygen through upconversion luminescence (UCL) to inhibit macrophage M1 polarization, and downregulates pro‐inflammatory cytokines IL‐6 and tumor necrosis factor‐α (TNF‐α), thereby repairing myocardial injury. To sum up, a photoresponsive upconversion cyanobacterium nanocapsule is developed, which can achieve MI prevention and treatment for only one injection via NIR‐defined respiration and photosynthesis.
Assembly: A Key Enabler for the Construction of Superior Silicon‐Based Anodes
Authors: Jiang Miaomiao , Chen Junliang , Zhang Yingbing , Song Nan , Jiang Wan , Yang Jianping
Published: September 2022

Silicon (Si) is regarded as the most promising anode material for high‐energy lithium‐ion batteries (LIBs) due to its high theoretical capacity, and low working potential. However, the large volume variation during the continuous lithiation/delithiation processes easily leads to structural damage and serious side reactions. To overcome the resultant rapid specific capacity decay, the nanocrystallization and compound strategies are proposed to construct hierarchically assembled structures with different morphologies and functions, which develop novel energy storage devices at nano/micro scale. The introduction of assembly strategies in the preparation process of silicon‐based materials can integrate the advantages of both nanoscale and microstructures, which significantly enhance the comprehensive performance of the prepared silicon‐based assemblies. Unfortunately, the summary and understanding of assembly are still lacking. In this review, the understanding of assembly is deepened in terms of driving forces, methods, influencing factors and advantages. The recent research progress of silicon‐based assembled anodes and the mechanism of the functional advantages for assembled structures are reviewed from the aspects of spatial confinement, layered construction, fasciculate structure assembly, superparticles, and interconnected assembly strategies. Various feasible strategies for structural assembly and performance improvement are pointed out. Finally, the challenges and integrated improvement strategies for assembled silicon‐based anodes are summarized.
Interfaced Structures between Halide Perovskites: From Basics to Construction to Optoelectronic Applications
Authors: Xiao Shuang , Qian Wei , Yang Shihe
Published: September 2022

The tsunami of research on halide perovskites over the last decade is sparked by the unexpected revelation of their singular properties, creating a new field of perovskite optoelectronics with great achievements. Soon recognized is the importance of perovskite–perovskite (pe–pe) interfaced structures with coherent interfaces on account of the ease with which to tailor perovskite semiconducting properties, and the prospect to inject new functions and boost device performance. There have been prominent developments in the pe–pe interfaced structures concerning their innovative construction strategies, distinctive properties, and interesting optoelectronic applications. This article provides an overview of recent advances on the pe–pe interfaced structures with a view to informing their rational design and guiding the improvement of the derivate devices. It begins with introduction of the structures, energy levels, band alignments, and ion migration pertaining to the pe–pe interfaced structures. Next, five synthetic approaches are systematically presented. Then, theories, simulations, and characterizations of the interfaced structures are discussed. This is followed by highlighting the distinctive applications of the pe–pe interfaced structures in solar cells, detectors, and light‐emitting diodes. Finally, the review is concluded by comprehensively summing up the key points covered and pointing out promising research directions along the line for future endeavors.
Accelerated Development of High Voltage Li‐Ion Cathodes
Authors: Jonderian Antranik , Jia Shipeng , Yoon Gabin , Cozea Victor Teodor , Galabi Nooshin Zeinali , Ma Sang Bok , McCalla Eric
Published: September 2022

High voltage cathodes are attractive for high energy density Li‐ion batteries. However, candidates such as LiCoPO4 have presented numerous challenges stemming from poor electronic/ionic conductivities such that typical solutions involving nanosizing result in extremely poor cycling performance. Here, high‐throughput methods are applied to develop near‐micron sized carbon‐coated LiCoPO4 with improved energy density and capacity retention. In total, 1300 materials with 46 different substituents are synthesized and characterized. A number of substituents show greatly improved capacity (e.g., 160 mAh g−1 for 1% indium (In) substitution vs 95 mAh g−1 for the pristine). However, co‐doping is required to improve extended cycling. Li1–3xCo1–2xInxMoxPO4 is found to be particularly effective with dramatically improved cycling (as high as 100% after 10 cycles, vs ≈50% in unsubstituted). While In improves the electronic conductivity of the carbon‐coated materials, molybdenum (Mo) co‐doping gives larger particles. DFT calculations show that Mo impedes the formation of Li/Co antisite defects.
ASBase: The universal database for aggregate science
Authors: Gong Junyi , Gong Wanjun , Wu Bo , Wang Haoran , He Wei , Dai Zhongyang , Li Yangzhong , Liu Yong , Wang Zhiming , Tuo Xiaojun , Lam Jacky W.Y. , Qiu Zijie , Zhao Zheng , Tang Ben Zhong
Published: September 2022

This paper reports the first universal and versatile database on aggregate materials for the field of aggregate science research. At the current stage, the database (http://119.91.135.188:8080/) contains over 1000 entries of organic aggregate material systems (mainly luminescent systems at the current stage) with a unique data structure which is designed particularly for aggregate materials and containing the photophysics and physicochemical properties of the compounds in different statuses of aggregation, including dilute solution form, pristine solid‐state, stable crystalline, and nanoaggregates formed in solvents. The web‐based interface of the database provided functions to index, search, manipulate, fetch and deposit data entries. In addition, a background calculation service optimizes the chemical structure of new entries on different levels of accuracies. The database also provided background API for interactive developments of prediction or regression models based on machine‐learning algorithms.
Incidence, age at diagnosis and survival with dementia across ethnic groups in England: A longitudinal study using electronic health records
Authors: Mukadam Naaheed , Marston Louise , Lewis Gemma , Mathur Rohini , Rait Greta , Livingston Gill
Published: September 2022

Introduction

We investigated the incidence of diagnosed dementia and whether age at diagnosis and survival afterward differs among the United Kingdom's three largest ethnic groups.

Methods

We used primary care electronic health records, linked Hospital Episode Statistics and mortality data for adults aged ≥65 years. We compared recorded dementia incidence 1997–2018, age at diagnosis, survival time and age at death after diagnosis in White, South Asian, and Black people.

Results

Dementia incidence was higher in Black people (incidence rate ratios [IRR] 1.22, 95% CI 1.15–1.30). South Asian and Black people with dementia had a younger age of death than White participants (mean difference for South Asian participants ‐2.97 years, (95% CI ‐3.41 to ‐2.53); and Black participants ‐2.66 years, (95% CI ‐3.08 to ‐2.24).

Discussion

South Asian and Black peoples’ younger age of diagnosis and death means targeted prevention and care strategies for these groups should be prioritized and tailored to facilitate take‐up.
Bright and Photostable Fluorescent Metal Nanocluster Supraparticles from Invert Emulsions
Authors: Zhou Shaochen , Peng Bo , Duan Yanyan , Liu Kai , Ikkala Olli , Ras Robin H. A.
Published: September 2022

Fluorescent supraparticles of gold, silver and copper nanoclusters are synthesized by simply drying of invert emulsions, resulting in a dozen‐fold increase in photoluminescence quantum yield (up to ≈80 %) and a significant improvement in photostability. The inhibition of the ligand twisting during the intramolecular charge transfer is found to be responsible for the enhancement, especially for the gold nanocluster supraparticles. This research provides a general, flexible, and easy method for producing highly luminescent and photostable metal nanocluster‐based materials that promise practical applications in white‐light‐emitting diodes.
Mechanistic Origin of Favorable Substituent Effects in Excellent Cu Cyclam Based HNO Sensors
Authors: Shi Yelu , Stella Gianna , Chu Jia‐Min , Zhang Yong
Published: September 2022

HNO has broad chemical and biomedical properties. Metal complexes and derivatives are widely used to make excellent HNO sensors. However, their favorable mechanistic origins are largely unknown. Cu cyclam is a useful platform to make excellent HNO sensors including imaging agents. A quantum chemical study of Cu cyclams with various substitutions was performed, which reproduced diverse experimental reactivities. Structural, electronic, and energetic profiles along reaction pathways show the importance of HNO binding and a proton‐coupled electron transfer mechanism for HNO reaction. Results reveal that steric effect is primary and electronic factor is secondary (if the redox potential is sufficient), but their interwoven effects can lead to unexpected reactivity, which looks mysterious experimentally but can be explained computationally. This work suggests rational substituent design ideas and recommends a theoretical study of a new design to save time and cost due to its subtle effect.
Vapor‐Triggered Mechanical Actuation in Polymer Composite Films Based on Crystalline Organic Cages
Authors: Alimi Lukman O. , Fang Fang , Moosa Basem , Ding Yanjun , Khashab Niveen M.
Published: September 2022

The fabrication of smart materials, which can efficiently mimic biological systems through the introduction of soft components, is of great importance in the emerging fields of sensors and actuators. Herein, a smart composite film that can mechanically respond to vapors trigger then readily restores its original shape upon the removal of the stimuli is reported. This actuating composite film was prepared by mixing the highly elastic poly (vinylidene fluoride) (PVDF) polymer with the flexible and crystalline organic cages (Oba‐cage) at variable concentrations. The mechanism of the mechanical response could be accurately recorded due to the ordered cage crystals. This work highlights the importance of designing smart materials at the molecular level to precisely control the response or reaction upon the introduction of different triggers, which can ultimately lead to a monumental leap in the field of soft robotics.
Navigating PFAS Treatment With GAC and Ion Exchange
Authors: Brown Douglas , LeBlanc Alan
Published: September 2022

Key Takeaways

The concentration and composition of per‐ and polyfluoroalkyl substances (PFAS) in source water and treated water goals are the main drivers affecting PFAS management.

Separately or together, granular activated carbon and ion exchange media are effective treatment options when trying to minimize PFAS in finished water.

Requirements for ultimate disposal or destruction of PFAS and process residuals significantly affect operating costs, which in turn play a critical role in treatment process selection.
Development of a New Crosslinked Highly Conductive Hybrid Electrolyte based on Polyetherdiamine, Diphenylmethane Diisocyanate and Organosilanes for Efficient Lithium‐Metal Battery
Authors: Saikia Diganta , Deka Juti Rani , Zeng Yu‐Hao , Chen Yi‐Ching , Kao Hsien‐Ming , Yang Yung‐Chin
Published: September 2022

In this study, a new crosslinked organic‐inorganic hybrid polymer electrolyte membrane is developed by first reacting polyetherdiamine with diphenylmethane diisocyanate, followed by addition of organosilane precursors 3‐(glycidyloxypropyl) trimethoxysilane and 2‐[methoxy(polyethyleneoxy) propyl] trimethoxysilane and LiClO4 salt. Various characterization methods are employed to probe the crystallinity behavior, morphology, ionic interactions, thermal stability, architectural durability and dynamic performance of the hybrid solid polymer electrolyte (HSPE) membranes. Among the electrolytes, the HSPE membrane with [EO]/[Li] ratio of 32 delivers the excellent ionic conductivity value of 1.2×10−4 S cm−1 at 30 °C. When the hybrid membrane without salt is plasticized with various electrolyte solvents, the ionic conductivity enhances significantly to values in the range of 1.2 to 1.8×10−3 S cm−1 at 30 °C. The lithium metal battery (LMB) assembled with the gel polymer electrolyte (GPE), lithium anode and LiFePO4 cathode provides excellent rate and cycle performances. The LMB delivers very stable discharge capacity of 121.1 mAh g−1 after 150 cycles at the rate of 0.1 C with 97.6 % capacity holding compared to first cycle and exhibits above 99 % Coulombic efficiency values. The present crosslinked hybrid polymer electrolytes are potentially promising for the future development of high performance lithium‐metal batteries.
Sustainability assessment of a decentralized green diesel production in small‐scale biorefineries
Authors: Salvador Guilherme V. , Salim Vera Maria M. , Toniolo Fabio S.
Published: September 2022

In this study, three scales of a biofuel‐driven biorefinery were evaluated in techno‐economic, environmental and geospatial terms for green diesel production from macauba oil. The results show that the relative capital expenditure on the small scale is four times higher than that on the large scale, being significantly affected by the hydrogen facilities. However, coproducts, tax deductions for family farming and carbon credits can sustain the small‐scale production of green diesel. The carbon footprint of the green diesel is lower than that of commercial biofuels. Finally, the geospatial analysis applied in Brazil reveals that macauba cultivation with low land‐use impact can be implemented near small‐scale biorefineries for local consumer markets. Therefore, the feasibility of the small scale depends on coproducts, public policies, decentralized hydrogen production and catalysts for low‐hydrogen demand routes. This biorefinery concept can decentralize the biofuel sector and make use of several types of biomasses besides macauba, generating socio‐economic and environmental gains. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.
Simulation of collective pursuit‐evasion behavior with runtime situational awareness
Authors: Yu Zhenjing , Tan Junyin , Li Sheng
Published: September 2022

We present a simulation method of pursuit‐evasion behaviors between different herds with runtime situational awareness. We model the collective movement of predators and prey in the hunting process based on an improved Boid model and the finite state machine involving multiple perception factors about the situations. Taking wolves hunting caribous as an example, our method not only simulates the collective behavior, but also realizes individual intelligent behaviors consistent with the observations. We conducted intensive experiments, and the results show that our method can simulate more realistic pursuit‐evasion behavior under different testing scenarios with a variety of parameters. Our method can be easily transferred to the theoretical study of collective behaviors of other herds.
Lipase‐Catalysed Enzymatic Kinetic Resolution of Aromatic Morita‐Baylis‐Hillman Derivatives by Hydrolysis and Transesterification
Authors: Mathebula Nompumelelo P. , Sheldon Roger A. , Bode Moira L.
Published: September 2022

Acylated Morita‐Baylis‐Hillman (MBH) adducts were synthesised and subjected to enzymatic kinetic resolution (EKR) by hydrolysis employing various lipase enzymes: from P. fluorescens, P. cepacia (PCL), C. antarctica A (CAL−A), C. antarctica B (CAL−B) and Novozyme 435. In a number of instances enantiopure Morita‐Baylis‐Hillman acetates or butyrates and their corresponding hydrolysed MBH adducts were obtained with ee values of >90 %, at ca. 50 % conversion, corresponding to enantiomeric ratio (E) values of >200. Enantioselective transesterification reactions on MBH adducts was achieved using acyl anhydrides in THF or the greener organic solvent 2‐MeTHF in the presence of CAL−A. This is the first report of successful lipase‐catalysed EKR of aromatic MBH adducts by transesterification in organic medium.
Predictive performance of J‐Calc‐CTO score for guidewire crossing through chronic total occlusion lesions within 30 minutes: J‐CTO score modified by computed tomography coronary angiography
Authors: Honda Yohsuke , Yamawaki Masahiro , Mori Shinsuke , Tsutsumi Masakazu , Makino Kenji , Chisiki Toshiki , Shirai Shigemitsu , Mizusawa Masafumi , Kobayashi Norihiro , Ito Yoshiaki
Published: September 2022

The original J‐CTO score predicts the difficulty of percutaneous coronary intervention (PCI) for chronic total occlusion (CTO) lesions, but the grade of calcification has not been fully evaluated. We examined 137 patients (141 CTO lesions) who underwent coronary computed tomography angiography (CTA) pre‐PCI between October 2016 and October 2021. They were randomly divided into derivation (n = 94) and validation (n = 47) groups. The degree and distribution of calcification in the occluded segment were assessed using CTA. The calcified index was defined as calcium volume divided by the length of the occluded segment. We created the J‐Calc‐CTO score consisting of calcification parameters associated with 30‐min wire crossing in the derivation group. The validity of the J‐Calc‐CTO score was compared with that of the original J‐CTO score using c‐statistics. The procedural success rate was 96%, and 30‐min wire crossing during the procedure was achieved in 29%. Dense calcification (calcified‐index >12) (odds ratio [OR]: 4.63; 95% confidence interval [CI]: 1.24–22.2; p = 0.04) and calcification in the center of the lumen (OR: 7.25; 95% CI: 1.48–32.1; p = 0.02) were independently associated with 30‐min wire crossing as variables evaluated using CTA. The J‐Calc‐CTO score was created by adding 1 point to the two parameters in place of “calcification” in the original J‐CTO score. The J‐Calc‐CTO score showed a higher predictive value of 30‐min wire crossing than the J‐CTO score in the derivation (c‐statistics; 0.836 vs. 0.670; p > 0.01) and validation groups (c‐statistics; 0.879 vs. 0.767, p > 0.01). The degree and distribution of calcification evaluated using CTA refined the predictive value of the original J‐CTO score for 30‐min wire crossing.
Piggyback mounting for stent and valve deployment during percutaneous pulmonary valve implantation
Authors: Zablah Jenny E. , Døhlen Gaute , Ystgaard Martin B. , Morgan Gareth J.
Published: September 2022

Objectives

We report our experience in simultaneously implanting multiple stents and valves mounted on a single balloon before and during transcatheter pulmonary valve placement.

Background

Heterogeneity and complexity of the right ventricular outflow tract (RVOT) may complicate stent deployment when preparing a landing zone for transcatheter pulmonary valve implantation.

Methods

Retrospective analysis of patients from Children's Hospital of Colorado, USA; and Oslo University Hospital, Norway, undergoing transcatheter pulmonary valve replacement that had at least two stents mounted on a single balloon, deployed in the RVOT.

Results

Over a 42‐month period, a total of 50 subjects from the two centers met inclusion criteria for the study. Subjects were predominantly male (58%), and the median age was 17 years (4–78 years). In six subjects (12%), there was need for prestenting with use of the double or triple stent piggyback technique. Forty subjects (80%) had a Melody ™ TPV implanted. In 45 cases (90%), one or more stents were mounted over the pulmonary valve using its delivery system, either the Ensemble for the Melody™ TPV or the Edwards Commander for the SAPIEN 3 THV. Thirty‐seven subjects (74%) had one stent mounted and eight subjects (16%) had two stents mounted over the pulmonary valve for simultaneous deployment. No complications related to this technique were reported.

Conclusions

The piggyback technique aims to simplify and facilitate adequate conduit preparation and valve insertion by minimizing manipulation across the outflow tract and decreasing the risk of stent distortion, misalignment, and embolization.
Functional Liquid Crystal Elastomers Based on Dynamic Covalent Chemistry
Authors: Valenzuela Cristian , Chen Yuanhao , Wang Ling , Feng Wei
Published: September 2022

The marriage of liquid crystal elastomers with dynamic covalent chemistry can be a new paradigm for the development of dynamic and intelligent polymers with versatile functionalities, which is of paramount significance for many emerging applications such as adaptive optics, soft robotics, bioinspired camouflage, 3D/4D printing technology and beyond. Read more in the Review by Wang, Feng et al. (10.1002/chem.202201957)
Electrochemical Dehydrogenative C−H Aminomethylation of Imidazopyridines and Related Heterocycles
Authors: Huang Raolin , Patureau Frederic W.
Published: September 2022

A facile and environmentally friendly electrochemical protocol is herein reported for the C(sp2)−C(sp3) cross dehydrogenative coupling between imidazopyridines and N,N‐dimethylanilines. The broad functional group compatibility includes halogens, ester, alcohol, sulfone as well as thiophene. This methodology is also suitable for benzo[d]imidazo[2,1‐b]thiazole, thiazoimidazole and tetrahydroisoquinoline, and can be scaled up to 5 mmol. Mechanistic insights are discussed.
Two Novel Three‐Dimensional Tetraphenylethylene‐Based Rare Earth MOFs with Ultra‐High Proton Conductivity and Performance Stability
Authors: Wang Shuyu , Zhao Lijia , Sun Hanxu , Wu Yuanyuan , Wang Ruidong , Zhang Suoshu , Du Lin , Zhao Qi‐Hua
Published: September 2022

In this work, the two example rare earth‐based metal‐organic frameworks (LaIII‐based MOFs), Eu‐ETTB and Gd‐ETTB, were obtained by self‐assembly. Both materials showed extremely high proton conductivity, with the proton conductivity of Eu‐ETTB being 1.53×10−2 S cm−1 at 98 % relative humidity (RH) and 85 °C and that of Gd‐ETTB being 2.63×10−2 S cm−1 at 98 % RH and 75 °C. This was almost the best performance observed for three‐dimensional porous MOFs without post‐synthetic modification and was based on milder conditions than for most materials. Furthermore, cycle test experiments and continuous work tests showed that both materials had excellent performance both in terms of stability and durability. Water vapor adsorption experiments showed that a large number of water molecules are adsorbed the hydrogen‐bond network's being rebuilt by the adsorbed water molecules in the pore channel and thus optimizing the channels for proton transfer explained the MOF's high performance.
Influence of Sulfur Atoms on TADF Properties from Through‐Space Charge Transfer Excited States
Authors: Zhang Danwen , Jiang Chenglin , Wen Zhenhua , Feng Xingyu , Li Kai
Published: September 2022

The harnessing of heavy atom effect of chalcogen elements offers a way for boosting the thermally activated delayed fluorescence (TADF) of purely organic luminescent materials that can harvest triplet excitons. However, the conformational and electronic variations induced by the heavy and large atoms may also have adverse effects on the TADF properties. Herein, the design, synthesis, and structures of a new type of through‐space charge transfer (TSCT) emitters containing benzothiazino[2,3,4‐kl]phenothiazine (DPTZ) as the donor unit are reported. The influences of S atoms on the emission properties have been systematically investigated by means of theoretical simulations, electrochemical and spectroscopic studies. Although the presence of π‐stacking interactions and calculated spin‐orbit coupling (SOC) values are beneficial for TSCT‐TADF properties, the triplet TSCT states are uplifted to above the locally excited (LE) state of the acceptor moieties. As a result, the new emitters display longer delayed fluorescence lifetimes (τDF) of 255.0–114.3 μs and lower PLQYs of 45–61 % in comparison with the O‐containing congeners (τDF=26.9–6.8 μs; PLQYs=74–71 %). This work highlights that a full consideration of various effects is essential when making use of heavy chalcogen atoms for the design of TADF emitters.
Dynamic Timing Control of Molecular Photoluminescent Systems
Authors: Zong Zezhou , Zhang Qi , Qu Da‐Hui
Published: September 2022

Dynamic control of molecular photoluminescence offers chemical solutions to designing functional emissive materials. Although stimuli‐switchable molecular luminescent systems are well established, how to encode these dynamic emissive systems with a “timing” feature, that is, time‐dependent luminescent properties, remains challenging. This Concept aims to summarize the design principles of dynamic timing molecular photoluminescent systems by discussing the state‐of‐the‐art of this topic and the shaping of fabrication strategies at both the molecular and supramolecular levels. An outlook and perspectives are given to outline the future opportunities and challenges in the rational design and potential applications of these smart emissive systems.
Mechanistic and Kinetic Investigations of ON/OFF (Photo)Switchable Binding of Carbon Monoxide by Chromium(0), Molybdenum(0) and Tungsten(0) Carbonyl Complexes with a Pyridyl‐Mesoionic Carbene Ligand
Authors: Boden Pit J. , Di Martino‐Fumo Patrick , Bens Tobias , Steiger Sophie T. , Marhöfer Daniel , Niedner‐Schatteburg Gereon , Sarkar Biprajit
Published: September 2022

Invited for the cover of this issue are Gereon Niedner‐Schatteburg, Biprajit Sarkar and co‐worker at TU Kaiserslautern and the University of Stuttgart. The image depicts the selective dissociation of an axial CO from a metal complex. Read the full text of the article at 10.1002/chem.202201038.
Antimalarial and Anticancer Activity Evaluation of Bridged Ozonides, Aminoperoxides, and Tetraoxanes
Authors: Coghi Paolo , Yaremenko Ivan A. , Prommana Parichat , Wu Jia Ning , Zhang Rui Long , Ng Jerome P. L. , Belyakova Yulia Yu. , Law Betty Yuen Kwan , Radulov Peter S. , Uthaipibull Chairat , Wong Vincent Kam Wai , Terent'ev Alexander O.
Published: September 2022

Bridged aminoperoxides, for the first time, were investigated for the in vitro antimalarial activity against the chloroquine‐resistant Plasmodium falciparum strain K1 and for their cytotoxic activities against immortalized human normal liver (LO2) and lung (BEAS‐2B) cell lines as well as human liver (HepG2) and lung (A549) cancer cell lines. Aminoperoxides exhibit good cytotoxicity against lung A549 cancer cell line. Synthetic ozonides were shown to have high activity against the chloroquine‐resistant P. falciparum. A cyclic voltammetry study of peroxides was performed, and most of the compounds did not show a direct correlation in oxidative capacity‐activity. Peroxides were analyzed for ROS production to understand their mechanism of action. However, none of the compounds has an impact on ROS generation, suggesting that ozonides induce apoptosis in HepG2 cells through ROS‐independent dysfunction pathway.
Development and validation of an RNA sequencing–based classifier for medullary thyroid carcinoma on thyroid FNA
Authors: Lubin Daniel J. , Sadow Peter M.
Published: September 2022

This commentary describes the development and validation of the Afirma RNA sequencing–based classifier for medullary thyroid carcinoma (MTC). The importance of the early diagnosis of MTC is discussed along with the limitations of cytomorphology alone.
Effect of Meal Timings and Meal Content on the AUC0‐12h of Mycophenolic Acid: A Simulation Study
Authors: Qian Lixuan , Jiao Zheng , Zhong Mingkang
Published: September 2022

Meal timings and content related to gallbladder emptying in the enterohepatic circulation are important for explaining the high variability in mycophenolic acid exposure. The limited sampling strategy (LSS) was established to estimate the area under the plasma concentration–time curve from time 0 to 12 hours (AUC0‐12h) of mycophenolic acid in therapeutic drug monitoring. The aim of this study is to investigate the effect of meal timings and content on the AUC0‐12h of mycophenolic acid and to assess the influence of meals on LSS. A mycophenolic acid pharmacokinetic model with a mechanism‐based enterohepatic circulation process was employed to perform simulations under various assumed meal scenarios. The simulations were compared to evaluate the effect of meal timings and meal content on mycophenolic acid AUC0‐12h. Monte Carlo simulations were performed using the meal parameter with the greatest impact on mycophenolic acid AUC0‐12h as a variable. The corresponding LSS equations were established, and the predictive performance was assessed. Both the meal timings and meal content affected the mycophenolic acid AUC0‐12h, and the postdose fasting period had the greatest impact. The predictive performance of the LSS is sensitive to the postdose fasting period. Therefore, meal timings may improve the estimation of mycophenolic acid AUC0‐12h and the efficacy of therapeutic drug monitoring.
Self‐Transportation of Superparamagnetic Droplets on a Magnetic Gradient Slippery Surface with On/Off Sliding Controllability
Authors: Hu Dongdong , Lai Hua , Liu Yuyan , Luo Xin , Song Yingbin , Zhang Dongjie , Fan Zhimin , Xie Zhimin , Cheng Zhongjun
Published: September 2022

Recently, research about droplet self‐transportation on slippery surfaces has become a hotspot. However, to achieve on/off sliding control during the self‐transportation process is still difficult. Herein, we report a magnetic slippery surface, and demonstrate on/off sliding control during the self‐transportation of superparamagnetic droplets. The surface is prepared through integrating a substrate that has a gradient magnetic region with a layer of paraffin infused hydrophobic SiO2 nanoparticles. On the surface, a superparamagnetic droplet is pinned at room temperature (about 25 °C), while it can self‐transport directionally as the temperature is increased to about 70 °C. When the temperature is cooled down again, the droplet would return to the pinned state, indicating that on/off sliding control during the self‐transportation process can be achieved. Furthermore, based on the excellent controllability, controllable coalescence of two droplets from opposite direction is displayed, demonstrating its potential application in numerous areas.
Plasma biomarkers predict cognitive trajectories in an ethnoracially and clinically diverse cohort: Mediation with hippocampal volume
Authors: Sapkota Shraddha , Erickson Kelsey , Harvey Danielle , Tomaszewski‐Farias Sarah E. , Olichney John M. , Johnson David K. , Dugger Brittany N. , Mungas Dan M. , Fletcher Evan , Maillard Pauline , Seshadri Sudha , Satizabal Claudia L. , Kautz Tiffany , Parent Danielle , Tracy Russell P. , Maezawa Izumi , Jin Lee‐Way , DeCarli Charles
Published: September 2022

Introduction

We examine whether the association between key plasma biomarkers (amyloid β [aβ] 42/40, total tau (t‐tau), neurofilament light [NfL]) and cognitive trajectories (executive function [EF] and episodic memory [EM]) is mediated through neurodegeneration.

Methods

All participants were recruited from the University of California, Davis‐Alzheimer's Disease Research Center (n = 473; baseline age range = 49—95 years, 60% women). We applied an accelerated longitudinal design to test latent growth models for EF and EM, and path and mediation analyses. Age was centered at 75 years, and all models were adjusted for sex, education, and ethnicity.

Results

HV differentially mediated the association aβ 42/40 and NfL on EF and EM level and change. Hippocampal volume (HV) did not mediate the association between t‐tau and cognitive performance.

Discussion

Neurodegeneration as represented with HV selectively mediates the association between key non‐invasive plasma biomarkers and cognitive trajectories in an ethnoracially and clinically diverse community‐based sample.
Informed Consent for Placebo‐Controlled Trials: Do Ethics and Science Conflict?
Authors: Feldman Hope A. , Feldman James A. , Miller Charles C. , Walsh Garrett , Tyson Jon E.
Published: September 2022

The use of a placebo has been considered the best method for controlling bias in a prospective randomized clinical trial and provides the most rigorous test of treatment efficacy for evaluating a medical therapy. Placebos commonly produce clinically important effects particularly in studies where the primary outcomes are subjective. Yet the potential beneficial or harmful effects of placebos are often not addressed in designing a clinical trial, calculating the sample size, seeking consent, or interpreting clinical trial results. In this manuscript, we use an actual study to indicate three approaches that might be considered in seeking informed consent for placebo‐controlled trials, and we explore the fundamental ethical and scientific complexities involved with each.
Trade‐off between plant resistance and tolerance to herbivory: Mechanical defenses outweigh chemical defenses
Authors: Salgado‐Luarte Cristian , González‐Teuber Marcia , Madriaza Karina , Gianoli Ernesto
Published: September 2022

Plant resistance includes mechanical and chemical defenses that reduce herbivory, whereas plant tolerance reduces the fitness impact of herbivory. Because defenses are costly and investing in both resistance and tolerance may be superfluous, trade‐offs among them are expected. In forest ecosystems, the mechanical strengthening of leaves is linked both to shade adaptation and antiherbivore defenses, but it also compromises resource uptake, therefore limiting regrowth following damage, suggesting a trade‐off between mechanical defenses and tolerance. We tested for the resistance–tolerance trade‐off across 11 common tree species in a temperate rainforest and explored mechanistic explanations by measuring chemical and mechanical defenses. Herbivory damage was negatively associated with leaf toughness and fiber content, whereas there was no significant relationship between herbivory and secondary metabolites (flavonols, gallic acid, tannins, and terpenoids). We detected a resistance–tolerance trade‐off, as expected. We found a negative relationship between mechanical defenses and tolerance, estimated as the survival ratio between experimentally damaged and undamaged seedlings. Tolerance and secondary metabolites showed no significant association. Results suggest that selective forces other than herbivory acting on defensive traits can favor a resistance–tolerance trade‐off. Therefore, plant adaptation to contrasting light environments may contribute to the evolution of resistance–tolerance trade‐offs.
Long‐term mortality in heart failure with mid‐range ejection fraction: systematic review and meta‐analysis
Authors: Raja Deep Chandh , Samarawickrema Indira , Das Souvik , Mehta Abhinav , Tuan Lukah , Jain Sanjiv , Dixit Sanjay , Marchlinski Frank , Abhayaratna Walter P. , Sanders Prashanthan , Pathak Rajeev K
Published: September 2022

Aims

Heart failure patients with mid‐range ejection fraction (HFmrEF) have overlapping clinical features, compared with patients with reduced ejection fraction (HFrEF) and preserved ejection fraction (HFpEF). We aim to perform a meta‐analysis of studies reporting long‐term outcomes in HFmrEF compared with HFrEF and HFpEF.

Methods and results

Data from 18 eligible large‐scale studies including 126 239 patients were pooled. Patients with HFmrEF had a lower risk of all‐cause death than those with HFrEF [risk ratio (RR) = 0.92; 95% CI = 0.85–0.98; P < 0.001]. This significant difference was seen in the follow‐up at 1, 2, and 3 years. Patients with HFmrEF had significantly lower risk of cardiovascular (CV) deaths than HFrEF (RR = 0.77; 95% CI = 0.65–0.92; P < 0.001). Subgroup analysis showed that studies recruiting >50% of males had higher risk of deaths with HFrEF (RR = 1.15; 95% CI = 1.04–1.26; P = 0.006). When compared with HFpEF, patients with HFmrEF had comparable risk of all‐cause death (RR = 1.02; 95% CI = 0.96–1.09; P = 0.53). Similarly, there were no differences in the 1, 2, and 3 year deaths; CV and non‐CV deaths were insignificant between HFmrEF and HFpEF.

Conclusions

The results of the study support that HFmrEF has better prognosis than HFrEF but similar prognosis when compared with HFpEF. Gender disparity between studies seems to influence the results between HFmrEF and HFrEF. Transition in left ventricular ejection fraction (LVEF), which could not be addressed in the study, may play a decisive role in determining outcomes. PROSPERO review registration number CRD42021277107.
An exploration of linkage fine‐mapping on sequences from case‐control studies
Authors: Nickchi Payman , Karunarathna Charith , Graham Jinko
Published: September 2022

Linkage analysis maps genetic loci for a heritable trait by identifying genomic regions with excess relatedness among individuals with similar trait values. Analysis may be conducted on related individuals from families, or on samples of unrelated individuals from a population. For allelically heterogeneous traits, population‐based linkage analysis can be more powerful than genotypic‐association analysis. Here, we focus on linkage analysis in a population sample, but use sequences rather than individuals as our unit of observation. Earlier investigations of sequence‐based linkage mapping relied on known sequence relatedness, whereas we infer relatedness from the sequence data. We propose two ways to associate similarity in relatedness of sequences with similarity in their trait values and compare the resulting linkage methods to two genotypic‐association methods. We also introduce a procedure to label case sequences as potential carriers or noncarriers of causal variants after an association has been found. This post hoc labeling of case sequences is based on inferred relatedness to other case sequences. Our simulation results indicate that methods based on sequence relatedness improve localization and perform as well as genotypic‐association methods for detecting rare causal variants. Sequence‐based linkage analysis therefore has potential to fine‐map allelically heterogeneous disease traits.
MoCA in five Indian languages: A brief screening tool to diagnose dementia and MCI in a linguistically diverse setting
Authors: Kaul Subhash , Paplikar Avanthi , Varghese Feba , Alladi Suvarna , Sharma Meenakshi , Dhaliwal R. S. , Goyal Sheetal , Saroja Aralikatte Onkarappa , Arshad Faheem , Divyaraj Gollahalli , Ghosh Amitabha , Iyer Gowri K. , J Sunitha , Khan Arfa Banu , Kandukuri Rajmohan , Mathew Robert , Mekala Shailaja , Menon Ramshekhar , Pauranik Apoorva , Nandi Ranita , Narayanan Jwala , Nehra Ashima , Padma M. V. , Ramakrishnan Subasree , Sarath Lekha , Shah Urvashi , Tripathi Manjari , Sylaja P. N. , Varma Ravi Prasad , Verma Mansi , Vishwanath Yeshaswini , Consortium I. C. M. R‐N. C. T. B
Published: September 2022

Introduction and Objectives

Early dementia diagnosis in low and middle‐income countries (LMIC) is challenging due to limited availability of brief, culturally appropriate, and psychometrically validated tests. Montreal Cognitive Assessment (MoCA) is one of the most widely used cognitive screening tests in primary and secondary care globally. In the current study, we adapted and validated MoCA in five Indian languages (Hindi, Bengali, Telugu, Kannada, and Malayalam) and determined the optimal cut‐off points that correspond to screening for clinical diagnosis of dementia and MCI.

Methods

A systematic process of adaptation and modifications of MoCA was fulfilled. A total of 446 participants: 214 controls, 102 dementia, and 130 MCI were recruited across six centers.

Results

Across five languages, the area under the curve for diagnosis of dementia varied from 0.89 to 0.98 and MCI varied from 0.73 to 0.96. The sensitivity, specificity and optimum cut‐off scores were established separately for five Indian languages.

Conclusions

The Indian adapted MoCA is standardized and validated in five Indian languages for early diagnosis of dementia and MCI in a linguistically and culturally diverse population.