bluuebunny/crossref_metadata_2025 huggingface dataset:
Experimental Investigation of Wave Force on the Pavement behind Crown Wall of Rubble Mound Seawall
Authors: Ko Haeng Sik , Lee Jooyeon , Jang Se-Chul , Oh Sang-Ho
Published: February 2022

Physical experiments were conducted to establish an empirical formula that predicts the wave force on the upside of the pavement behind crown wall of rubble mound seawall due to wave overtopping as well as the uplift force on the downside of the pavement. The experiments were performed by different conditions of the parapet, water depth, relative freeboard, and thickness of the armour layer. Then, the wave force on the upside and downside of the pavement behind the crown wall was analyzed. The parameters that affect the wave overtopping force and the uplift force were identified and empirical formulae were suggested for evaluating the forces on the pavement.
Remote Patient Monitoring During COVID-19
Authors: Pronovost Peter J. , Cole Melissa D. , Hughes Robert M.
Published: February 2022

This Viewpoint explains how some hospitals used home monitoring of pulse oximetry during the COVID-19 pandemic to avoid patient overcrowding and control high patient to staff ratios and how increased use of home monitoring for other vital signs could potentially improve patient safety and decrease costs.
Treasury Department cautions against alcohol mega‐mergers
Authors: Knopf Alison
Published: February 2022

This month, the U.S. Department of the Treasury, in consultation with the U.S. Department of Justice (DOJ) and the Federal Trade Commission (FTC), released a new report calling for more competition in the markets for beer, wine and spirits. On the one hand, the government is pleased about the entry of small businesses, but on the other, it is very concerned about the acquisition of these small businesses by the few big companies in the field.
Scalable Thousand Channel Penetrating Microneedle Arrays on Flex for Multimodal and Large Area Coverage BrainMachine Interfaces
Authors: Lee Sang Heon , Thunemann Martin , Lee Keundong , Cleary Daniel R. , Tonsfeldt Karen J. , Oh Hongseok , Azzazy Farid , Tchoe Youngbin , Bourhis Andrew M. , Hossain Lorraine , Ro Yun Goo , Tanaka Atsunori , Kılıç Kıvılcım , Devor Anna , Dayeh Shadi A.
Published: February 2022

The Utah array powers cutting‐edge projects for restoration of neurological function, such as BrainGate, but the underlying electrode technology has itself advanced little in the last three decades. Here, advanced dual‐side lithographic microfabrication processes is exploited to demonstrate a 1024‐channel penetrating silicon microneedle array (SiMNA) that is scalable in its recording capabilities and cortical coverage and is suitable for clinical translation. The SiMNA is the first penetrating microneedle array with a flexible backing that affords compliancy to brain movements. In addition, the SiMNA is optically transparent permitting simultaneous optical and electrophysiological interrogation of neuronal activity. The SiMNA is used to demonstrate reliable recordings of spontaneous and evoked field potentials and of single unit activity in chronically implanted mice for up to 196 days in response to optogenetic and to whisker air‐puff stimuli. Significantly, the 1024‐channel SiMNA establishes detailed spatiotemporal mapping of broadband brain activity in rats. This novel scalable and biocompatible SiMNA with its multimodal capability and sensitivity to broadband brain activity will accelerate the progress in fundamental neurophysiological investigations and establishes a new milestone for penetrating and large area coverage microelectrode arrays for brain–machine interfaces.
Smart µ‐Fiber Hydrogels with Macro‐Porous Structure for Sequentially Promoting Multiple Phases of Articular Cartilage Regeneration
Authors: Ma Zhijie , Song Wei , He Dan , Zhang Xin , He Yaohua , Li Haiyan
Published: February 2022

Hydrogels are widely utilized for articular cartilage regeneration. However, traditional hydrogels with nano‐sized pores lead to poor cell and tissue infiltration. Furthermore, hydrogels that can stimulate each phase of cartilage regeneration to enhance cartilage repair are highly demanded. Herein, a macro‐porous hydrogel is fabricated by crosslinking mixed sodium alginate (SA) and hyaluronic acid (HA) solution into SA/HA micro‐fibers (µ‐fibers) first and subsequently crosslinking the µ‐fibers into hydrogel blocks. Besides, exosomes derived from NR8383 cells activated by lipopolysaccharides (LPS) and stimulated with bioglass (BG) ion extracts (LPS/BG‐exo) are incorporated into the hydrogel as they exhibit a strong ability to regulate inflammation homeostasis and recruit bone marrow mesenchymal stem cells (BMMSCs). Meanwhile, poly (lactic‐co‐glycolic acid) (PLGA) microspheres containing kartogenin (KGN) (PLGAKGN) are encapsulated within the hydrogel for inducing the chondrogenic differentiation of recruited BMMSCs when KGN is released after the LPS/BG‐exo. Thus, the obtained macro‐porous SA/HAexo‐PLGAKGN hydrogel can not only significantly improve the infiltration of tissues into the hydrogel but also sequentially deliver LPS/BG‐exo and KGN to enhance the cartilage regeneration in a rat cartilage defect model. Prospectively speaking, the SA/HAexo‐PLGAKGN hydrogel is a potential candidate for other tissue regeneration as the bioactive substances can be adjusted according to different purposes.
High‐Temperature Confinement Synthesis of Supported Pt–Ni Nanoparticles for Efficiently Catalyzing Oxygen Reduction Reaction
Authors: Wang Kun , Wang Yifan , Geng Shipeng , Wang Yi , Song Shuqin
Published: February 2022

Developing efficient Pt‐based alloy as oxygen reduction reaction (ORR) electrocatalysts is critical for practical applications of fuel cells. High‐temperature reduction technology can improve the alloy atoms ordering but inevitably accelerate metal sintering. Here, Pt–Ni nanoparticles (<5 nm) embedded into ordered mesoporous carbon (OMC) matrix are developed, and its confinement effect suppresses nanoparticles sintering up to 900 °C. After an elaborative dealloying process, the surface structure of Pt–Ni nanoparticles changes from a Ni‐rich to Pt‐rich layer (the thickness is about 0.15 nm). The optimized sample (PtNi3@OMC‐A) displays outstanding mass and specific activities of 2.11 A mgPt–1 and 3.23 mA cmPt–2, more than one order of magnitude higher than commercial Pt/C (20 wt%). PtNi3@OMC‐A also exhibits long‐term stability with a negligible activity loss after 10 000 potential cycles. Both experimental results and density functional theory calculations reveal that alloying effect as well as strain effect weaken Pt–O binding strength, thus resulting in an outstanding ORR activity. Furthermore, the high long‐term stability can be attributed to the confinement of OMC, inhibiting the detachment or agglomeration of the embedded alloy nanoparticles.
Heterointerface Created on Au‐Cluster‐Loaded Unilamellar Hydroxide Electrocatalysts as a Highly Active Site for the Oxygen Evolution Reaction
Authors: Kitano Sho , Noguchi Tomohiro G. , Nishihara Masamichi , Kamitani Kazutaka , Sugiyama Takeharu , Yoshioka Satoru , Miwa Tetsuya , Yoshizawa Kazunari , Staykov Aleksandar , Yamauchi Miho
Published: February 2022

The oxygen evolution reaction (OER) is a critical element for all sorts of reactions that use water as a hydrogen source, such as hydrogen evolution and electrochemical CO2 reduction, and novel design principles that provide highly active sites on OER electrocatalysts push the limits of their practical applications. Herein, Au‐cluster loading on unilamellar exfoliated layered double hydroxide (ULDH) electrocatalysts for the OER is demonstrated to fabricate a heterointerface between Au clusters and ULDHs as an active site, which is accompanied by the oxidation state modulation of the active site and interfacial direct OO coupling (“interfacial DOOC”). The Au‐cluster‐loaded ULDHs exhibit excellent activities for the OER with an overpotential of 189 mV at 10 mA cm−2. X‐ray absorption fine structure measurements reveal that charge transfer from the Au clusters to ULDHs modifies the oxidation states of trivalent metal ions, which can be active sites on the ULDHs. The present study, supported by highly sensitive spectroscopy combining reflection absorption infrared spectroscopy and modulation‐excitation spectroscopy and density functional theory calculations, indicates that active sites at the interface between the Au clusters and ULDHs promote a novel OER mechanism through interfacial DOOC, thereby achieving outstanding catalytic performance.
Piezochromic Luminescence of Cyano Substituted E/Z Isomeric Derivatives: Different Responses to External Stimuli
Authors: Gao Lei , Bi Changjiang , Liu Futong , Feng Zijun , Sun Chenglin , Xu Shuping , Xu Weiqing , Lu Ping
Published: February 2022

As an important class of stimuli‐responsive material, piezochromic organic materials have been widely investigated in recent years. To promote their further applications as pressure sensors, realizing a high sensitivity and big color contrast, especially under high external pressure, is of great importance. Herein, two pure cis/trans isomers, E‐ANTCN and Z‐ANTCN, based on anthracene and cyano substituted double bond are achieved. The molecular structures are determined by nuclear Overhauser effect spectroscopy, correlation spectroscopy, and X‐ray diffraction. At ambient conditions, both of them show typical mechanochromic characteristics under grinding−heating or grinding−fuming treatments. E‐ANTCN displays a sensitivity of 0.83 nm GPa−1 and a color contrast of 5 nm in a high‐pressure experiment, while Z‐ANTCN shows a much enhanced sensitivity of 22.64 nm GPa−1 and bigger color contrast of 110 nm, indicating the potential as a good colorimetric sensor for external pressure. The two cyano groups in the same side of double bond in Z‐ANTCN induce more intense intermolecular interactions with a resultant spatial packing mode being mainly responsive for its good sensing performance. This study fills the gap for a piezochromic property and high‐pressure experiment of E/Z isomers and provides useful information for the investigation of molecular structural changes under isotropic and anisotropic treatments.
Vacuum Ultraviolet (120–200 nm) Avalanche Photodetectors
Authors: Jia Lemin , Huang Feng , Zheng Wei
Published: February 2022

Ultra‐sensitive photodetectors that can operate at vacuum ultraviolet (VUV) wavelengths are greatly needed in space exploration as well as photolithography sensing and imaging. Traditional photomultiplier tubes for weak VUV light detection have the characteristics of large physical volume and high working voltage, and thus, the development of ultra‐wide‐bandgap semiconductor‐based avalanche photodetectors (APD) with advantages of miniaturization, radiation resistance, and filter‐free characteristics is urgently needed. Here, this work reports the details and results of APDs prepared for VUV detection based on high‐quality AlN heterojunctions. An extremely low dark current of ≈30 fA is achieved, and appreciable spectral response in the range of 120–220 nm and a gain >4000 at room temperature are demonstrated for the first time. Such APDs with integrability are attractive for single‐photon detection and imaging at VUV wavelengths in the future.
Hybrid Inorganic–Organic Luminescent Supraparticle Taggants with Switchable Dual‐Level ID
Authors: Miller Franziska , Reichstein Jakob , Mandel Karl
Published: February 2022

Tracking and tracing of objects are of paramount importance for realizing a Circular Economy and can be achieved by incorporating micrometer‐scaled luminescent identification (ID) taggants. While established systems are passive, displaying merely an ID feature, for monitoring a products’ life cycle, conscious taggants with stimuli‐triggered switchable ID signals, e.g., to record a recycling step, are desired. Herein, micrometer‐scaled hybrid inorganic–organic taggants with a temperature‐triggered switchable luminescent ID are reported. They are produced by assembling eight different types of organic and inorganic nanoparticles (NPs) via a two‐step spray‐drying process into supraparticles (SPs) with a core–shell structure. This hierarchical structure and well‐balanced mass‐ratios of the utilized nanosized building blocks are key to controlling the occurring coupling effects within SPs, thus, to obtain the switchable ID functionality. Initially, the temperature‐inert inorganic luminescent ID‐level, located in the core, is concealed by a mutable organic ID‐level, emitted by the shell. Upon specific heat treatment, the ID is switched by irreversible quenching of the organic ID‐level, revealing the inorganic ID‐level. Furthermore, both ID‐levels are read out ratiometrically using the same excitation wavelength for their detection. Based on the SPs’ toolbox‐like manufacturing, the ID signals are adjustable to yield the demanded code variety on both ID‐levels.
Synthesis and Characterization of a LiFe0.6Mn0.4PO4 Olivine Cathode for Application in a New Lithium Polymer Battery
Authors: Minnetti Luca , Marangon Vittorio , Hassoun Jusef
Published: February 2022

A LiFe0.6Mn0.4PO4 (LFMP) cathode exploiting the olivine structure is herein synthesized and characterized in terms of structure, morphology, and electrochemical features in a lithium cell. The material shows reversibility of the electrochemical process which evolves at 3.5 and 4 V versus Li+/Li due to the Fe+2/Fe+3 and Mn+2/Mn+3 redox couples, respectively, as determined by cyclic voltammetry. The LFMP has a well‐defined olivine structure revealed by X‐ray diffraction, a morphology consisting of submicron particle aggregated into micrometric clusters as indicated by scanning and transmission electron microscopy, with a carbon weight ratio of about 4% as suggested by thermogravimetry. The electrode is used in lithium cells subjected to galvanostatic cycling with a conventional liquid electrolyte, and demonstrates a maximum capacity of 130 mAh g−1, satisfactory rate capability, excellent efficiency, and a stable trend. Therefore, the material is studied in a lithium metal polymer cell exploiting an electrolyte based on polyethylene glycol dimethyl ether with a solid configuration. The cell reveals very promising features in terms of capacity, efficiency, and retention, and suggests the LFMP material as a suitable electrode for polymer batteries characterized by increased energy density and remarkable safety.
Bifacial Modulation of Carrier Transport in BiVO4 Photoanode for Stable Photoelectrochemical Water Splitting via Interface Engineering
Authors: Mane Pratik , Bagal Indrajit V. , Bae Hyojung , Burungale Vishal , Seong Chaewon , Ryu Sang‐Wan , Ha Jun‐Seok
Published: February 2022

Monoclinic bismuth vanadate photoanodes promise high efficiency‐to‐cost ratios for photoelectrochemical (PEC) water splitting owing to their suitable band structure and ease of synthesis. However, inadequate charge separation and sluggish oxidation kinetics remain a fundamental challenge. This study investigates bifacially interface engineered BiVO4 photoanodes by considering a seed‐layer and NiOOH oxygen evolution catalyst (OEC) over‐layer to regulate the charge carrier transport and improve the overall PEC water‐splitting performance. The modification of the BiVO4/FTO interface stimulates electron flow towards fluorine‐doped tin oxide (FTO) and a NiOOH over‐layer improves the facile hole transfer from BiVO4 to the electrolyte. Compared to the moderate photocurrent density of a bare BiVO4 photoanode (1.5 mA cm−2), the interface‐engineered Seed_BiVO4_NiOOH photoanode shows a remarkably high (≈3.4 times higher) photocurrent density of 5.10 mA cm−2 at 1.23 V vs reversible hydrogen electrode with impressive long‐term stability over 9 h under illumination. The optimally interface engineered Seed_BiVO4_NiOOH photoanode shows an excellent photoconversion efficiency (1.83%), with significant improvement in bulk charge separation efficiency. This work presents a promising strategy for the development of a highly stable PEC water‐splitting device and eliminates the intrinsic material shortcomings of the bare BiVO4 photoanode by modulating the carrier transport via bifacial interface engineering.
Self‐Healing Mechanism of Lithium in Lithium Metal
Authors: Jiao Junyu , Lai Genming , Zhao Liang , Lu Jiaze , Li Qidong , Xu Xianqi , Jiang Yao , He Yan‐Bing , Ouyang Chuying , Pan Feng , Li Hong , Zheng Jiaxin
Published: February 2022

Li is an ideal anode material for use in state‐of‐the‐art secondary batteries. However, Li‐dendrite growth is a safety concern and results in low coulombic efficiency, which significantly restricts the commercial application of Li secondary batteries. Unfortunately, the Li‐deposition (growth) mechanism is poorly understood on the atomic scale. Here, machine learning is used to construct a Li potential model with quantum‐mechanical computational accuracy. Molecular dynamics simulations in this study with this model reveal two self‐healing mechanisms in a large Li‐metal system, viz. surface self‐healing, and bulk self‐healing. It is concluded that self‐healing occurs rapidly in nanoscale; thus, minimizing the voids between the Li grains using several comprehensive methods can effectively facilitate the formation of dendrite‐free Li.
Real‐Time Correlation Detection via Online Learning of a Spiking Neural Network with a Conductive‐Bridge Neuron
Authors: Kim Dong‐Won , Woo Dae‐Seong , Kim Hea‐Jee , Jin Soo‐Min , Jung Sung‐Mok , Kim Dong‐Eon , Kim Jae‐Joon , Shim Tae‐Hun , Park Jea‐Gun
Published: February 2022

The neuronal density of complementary metal‐oxide‐semiconductor field‐effect transistor‐based neurons is limited because of the use of capacitors. Therefore, a novel neuron is fabricated using a conductive‐bridge‐neuron device, current‐mirror‐type sense amplifier, latch, micro‐controller‐unit, and digital‐analog‐converters. This neuron exhibits a typical integrate‐and‐fire function; in particular, the generation frequency of the fire spikes at the neuron exponentially increases with the input‐voltage‐spike amplitude. Using the proposed designed neuron in combination with an input spike generation and spike‐timing‐dependent‐plasticity algorithm, a real‐time correlation detection based on online learning is realized. With the increase in the number of learning iterations, the weight of synapses for 100 correlated input neurons gradually increase, whereas that for 900 uncorrelated input neurons steadily reduce. In addition, after 700 learning iterations, the output neuron is almost synchronized with the 100 correlated input neurons, thereby achieving correlation detection for cognitive functions in neuromorphic architectures and demonstrating the possibility of development of a neuromorphic chip based on the conductive‐bridge neurons and synapses.
Formulating noncovalent interactions to predict structural transition in mixed guest hydrates
Authors: Dongre Harshal J. , Jana Amiya K.
Published: February 2022

This work aims at formulating the noncovalent interactions of the mixed guest hydrate lattices of sI and sII structures. The reduced density plots obtained at the B3LYP level with 6‐31G(d) split valence set unveil the crucial contributions of hydrogen bonding, dispersion, van der Waals interaction, and steric effects toward lattice stability. These contributions are rather unreported in the hydrate phase equilibrium modeling. With this research gap, we attempt to formulate the natural regularity in the nonstoichiometric hydrates by the spherical harmonics shape descriptor. The van der Waals and hydrogen‐bond interactions are described with Kihara spherical cell potential and ab initio based calculations, respectively. Further, the ionization potential and polarizability of the guest molecule describe the dispersion interactions. Combining these contributions, we introduce a theoretical framework for the phase equilibrium modeling of mixed guest hydrates. This novel formulation offers various appealing advantages as: significantly reduced parametric structure, standardization of the parameter value for host–host pair, and generalized model framework. Despite of making the proposed theory so simple, it consistently outperforms the existing latest models, which employ various state equations, ab initio based calculations and CSMGem, for a wide variety of systems (total 26 systems tested) with reference to the experimental data.
Huriez syndrome: Additional pathogenic variants supporting allelism to SMARCAD syndrome
Authors: Loh Abigail Y. T. , Špoljar Sanja , Neo Granville Y. W. , Escande‐Beillard Nathalie , Leushacke Marc , Luijten Monique N. H. , Venkatesh Byrappa , Bonnard Carine , van Steensel Maurice A. M. , Hamm Henning , Carmichael Andrew , Rajan Neil , Carney Thomas J. , Reversade Bruno
Published: February 2022

Huriez syndrome (HRZ, OMIM181600) is a rare genodermatosis characterized by scleroatrophic hands and feet, hypoplastic nails, palmoplantar keratoderma, and predisposition to cutaneous squamous cell carcinoma (cSCC). We report herein three HRZ families from Croatia, the Netherlands, and Germany. Deep sequencing followed by Sanger validation, confirmed the presence of germline causative SMARCAD1 heterozygous pathogenic variants. All seven HRZ patients displayed hypohidrosis, adermatoglyphia, and one patient developed cSCC at 32 years of age. Two novel monoallelic germline mutations were identified which are predicted to disrupt the first exon‐intron boundary of the skin‐specific SMARCAD1 isoform. On the basis of phenotypic and genotypic convergence with Adermatoglyphia (OMIM136000) and Basan syndrome (OMIM129200), our results lend credence to the notion that these three Mendelian disorders are allelic. We propose adding Huriez syndrome to the previously suggested SMARCAD syndrome designation, which was originally invoked to describe the spectrum of monogenic disorders between Adermatoglyphia and Basan syndrome.
A comparison of four fetal biometry growth charts within an Australian obstetric population
Authors: Dry Candice , Pedretti Michelle K. , Nathan Elizabeth , Dickinson Jan E.
Published: February 2022

Purpose

The aim of this study was to investigate the applicability of four existing fetal growth charts to a local tertiary hospital obstetric population.

Method

Four existing fetal growth charts (the Raine study reference charts, INTERGROWTH‐21st charts, World Health Organization (WHO) fetal growth study charts and Australasian Society for Ultrasound in Medicine (ASUM) endorsed Campbell Westerway charts were compared using data from 11651 singleton pregnancy ultrasound scans at King Edward Memorial Hospital (KEMH). The 3rd, 10th, 50th 90th and 97th percentile curves for abdominal circumference (AC) biometry for the KEMH data were calculated and the four primary correlation parameters from fitted 3rd order polynomials (a, b, c and d) were used to generate like‐for‐like comparisons for all charts.

Results

The overall comparisons showed a significant variation with different growth charts, giving different percentiles for the same fetal AC measurement. INTERGROWTH‐21st percentile curves tended to fall below those of other charts for AC measurements. Both the Raine Study charts and ASUM charts were the charts of closest overall fit to the local data.

Conclusion

Our data show the Raine Study charts are the most appropriate for our population compared with the other three charts assessed suggesting the ‘one size fits all’ model may not be appropriate. However, additional analysis of biometry measurements, primarily AC, is needed to address the deficiency of data at 14‐18 weeks gestation which exists for the Raine Study data.

A reasonable alternative may be to adopt the WHO charts with local calibration (including the 14 ‐ 18 week gestation period).
Racial/ethnic disparities in initiation and persistent use of anti‐dementia medications
Authors: Zhu Carolyn W. , Neugroschl Judith , Barnes Lisa L. , Sano Mary
Published: February 2022

Background

Racial/ethnic disparities in anti‐dementia medications use in longitudinally followed research participants are unclear.

Methods

The study included initially untreated participants followed in National Alzheimer's Coordinating Center Uniform Data Set who were ≥65 at baseline with Alzheimer's disease dementia.

Outcomes

Outcomes for acetylcholinesterase inhibitor (AChEI) treatment included (1) any new AChEI treatment during follow‐up, and (2) persistence of treatment during follow‐up categorized into: intermittent treatment (< 50% follow‐ups reporting treatment), persistent (≥50% follow‐ups), and always treated. Outcomes for memantine treatment were similarly constructed.

Results

Controlling for participant characteristics, Black and Hispanic participants remained less likely than White participants to report any new AChEI or memantine treatment during follow‐up. Among those who reported new treatment during follow‐up, both Black and Hispanic participants were less likely than White participants to be persistently treated with AChEI and memantine.

Discussion

Substantial racial/ethnic treatment disparities remain in controlled settings of longitudinal research in which participants have access to dementia experts, suggesting wider disparities in the larger community.
The complex relationship between depression and progression to incident cognitive impairment across race and ethnicity
Authors: Babulal Ganesh M. , Zhu Yiqi , Roe Catherine M. , Hudson Darrell L. , Williams Monique M. , Murphy Samantha A. , Doherty Jason , Johnson Ann M. , Trani Jean‐Francois
Published: February 2022

Introduction

We examined baseline differences in depression and antidepressant use among cognitively normal older adults in five ethnoracial groups and assessed whether depression predicted a faster progression to incident cognitive impairment across groups.

Methods

Data from the National Alzheimer's Coordinating Center (n = 8168) were used to examine differences between non‐Hispanic Whites (nHW), African Americans (AA), Hispanics, Asians, and American Indian and Alaskan Natives in cross‐sectional and longitudinal models.

Results

AA had a lower risk of depression compared to nHW at baseline. No statistical interactions were noted between ethnoracial groups and depression. However, depression independently predicted a faster progression to incident cognitive impairment. Hispanics and Asian participants had a higher hazard for progression compared to nHW.

Discussion

Previously established risk factors between depression and dementia were not found among AA and nHW participants. The relationship between depression and ethnoracial groups is complex and suggests differential effects on progression from cognitive normality to impairment.
In Situ Halogen‐Ion Leaching Regulates Multiple Sites on Tandem Catalysts for Efficient CO2 Electroreduction to C2+ Products
Authors: Yang Ruoou , Duan Junyuan , Dong Panpan , Wen Qunlei , Wu Mao , Liu Youwen , Liu Yan , Li Huiqiao , Zhai Tianyou
Published: February 2022

Tandem catalysts can divide the reaction into distinct steps by local multiple sites and thus are attractive to trigger CO2RR to C2+ products. However, the evolution of catalysts generally exists during CO2RR, thus a closer investigation of the reconstitution, interplay, and active origin of dual components in tandem catalysts is warranted. Here, taking AgI−CuO as a conceptual tandem catalyst, we uncovered the interaction of two phases during the electrochemical reconstruction. Multiple operando techniques unraveled that in situ iodine ions leaching from AgI restrained the entire reduction of CuO to acquire stable active Cu0/Cu+ species during the CO2RR. This way, the residual iodine species of the Ag matrix accelerated CO generation and iodine‐induced Cu0/Cu+ promotes C−C coupling. This self‐adaptive dual‐optimization endowed our catalysts with an excellent C2+ Faradaic efficiency of 68.9 %. Material operando changes in this work offer a new approach for manipulating active species towards enhancing C2+ products.
Regio‐ and Enantioselective γ‐Allylic Alkylation of In Situ‐Generated Free Dienolates via Scandium/Iridium Dual Catalysis
Authors: Zhang Jian , Yang Wu‐Lin , Zheng Hanliang , Wang Yi , Deng Wei‐Ping
Published: February 2022

An unprecedented asymmetric γ‐allylic alkylation of free dienolates via Sc/Ir dual catalysis is reported, which affords a range of synthetically versatile γ‐allylic crotonaldehydes in high efficiency with excellent chemo‐, regio‐, and enantioselectivities. The dienolates bearing no essential auxiliary groups were generated in situ by scandium triflate‐mediated Meinwald rearrangement of vinyloxiranes atom‐economically. With the assistance of computational density functional theory calculations, a Sc/Ir bimetallic catalytic cycle was proposed to illustrate the reaction mechanism.
Real‐Time Monitoring of Dynamic Microbial Fe(III) Respiration Metabolism with a Living Cell‐Compatible Electron‐Sensing Probe
Authors: Chen Na , Du Na , Wang Wenjie , Liu Tiangang , Yuan Quan , Yang Yanbing
Published: February 2022

Monitoring microbial metabolism is vital for biomanufacturing processes optimization. However, it remains a grand challenge to offer insight into microbial metabolism due to particularly complex and dynamic processes. Here, we report an electron‐sensing probe Zn2GeO4:Mn@Fe3+ for real‐time and dynamic monitoring of Fe(III) respiration metabolism. The quenched persistent luminescence of Zn2GeO4:Mn@Fe3+ is recovered when Fe3+ accepted electrons from the dynamic Fe(III) respiration metabolism, enabling the real‐time monitoring of microbial metabolism. The probe shows the capability to verify the role of related biomolecules in microbial Fe(III) respiration metabolism, to track the dynamic Fe(III) respiration metabolic response to environmental stress and microbial co‐culture interactions. Furthermore, the Zn2GeO4:Mn@Fe3+ probe provides guidance for improving biosynthesis efficiency by monitoring Fe redox recycling in microbial co‐culture.
Cofactor‐Driven Cascade Reactions Enable the Efficient Preparation of Sugar Nucleotides
Authors: Zheng Yuan , Zhang Jiabin , Meisner Jeffrey , Li Wanjin , Luo Yawen , Wei Fangyu , Wen Liuqing
Published: February 2022

Glycosylation is catalyzed by glycosyltransferases using sugar nucleotides or occasionally lipid‐linked phosphosugars as donors. However, only very few common sugar nucleotides that occur in humans can be obtained readily, while the majority of sugar nucleotides that exist in bacteria, plants, archaea, or viruses cannot be synthesized in sufficient quantities by either enzymatic or chemical synthesis. The limited availability of such rare sugar nucleotides is one of the major obstacles that has greatly hampered progress in glycoscience. Herein we describe a general cofactor‐driven cascade conversion strategy for the efficient synthesis of sugar nucleotides. The described strategy allows the large‐scale preparation of rare sugar nucleotides from common sugars in high yields and without the need for tedious purification processes.
Synthesis of Molecular Phenylcalcium Derivatives: Application to the Formation of Biaryls
Authors: Pearce Kyle G. , Dinoi Chiara , Hill Michael S. , Mahon Mary F. , Maron Laurent , Schwamm Ryan S. , Wilson Andrew S. S.
Published: February 2022

Hydrocarbon‐soluble β‐diketiminato phenylcalcium derivatives, which display various modes of Ca−μ2‐Ph−Ca bridging, are accessible from reactions of Ph2Hg and [(BDI)CaH]2. Although the resultant compounds are inert toward the C−H bonds of benzene, they yield selective and uncatalyzed biaryl formation when reacted with readily available aryl bromides.
Photo‐Reduction with NIR Light of Nucleus‐Targeting PtIVNanoparticles for Combined Tumor‐Targeted Chemotherapy and Photodynamic Immunotherapy
Authors: Wei Dengshuai , Huang Yun , Wang Bin , Ma Lili , Karges Johannes , Xiao Haihua
Published: February 2022

The development of PtIVprodrugs which are selectively reduced within cancerous cells into their PtIItherapeutically active species has received increasing attention within the last decade. Despite recent research progress, the majority of investigated compounds are excited using ultraviolet or blue light. As the light penetration depth is low at these wavelengths, the treatment of deep‐seated or large tumors is limited. To overcome this limitation, herein, the example of PtIV‐functionalized nanoparticles that could be excited within the NIR region at 808 nm is reported. The polymer backbone which can self‐assemble into nanoparticles was functionalized with PtIVcomplexes for chemotherapy, photosensitizers for photodynamic immunotherapy, and nucleus/cancer‐targeting peptides. Upon irradiation, the PtIVcenter is reduced to PtIIand the axially coordinated ligands are released, presenting a multimodal treatment. While selectively accumulating in tumorous tissue, the nanoparticles demonstrated the ability to eradicate a triple‐negative breast cancer tumor inside a mouse model.
Selective Coupling of 1,2‐Bis‐Boronic Esters at the more Substituted Site through Visible‐Light Activation of Electron Donor–Acceptor Complexes
Authors: Wang Hui , Wu Jingjing , Noble Adam , Aggarwal Varinder K.
Published: February 2022

1,2‐Bis‐boronic esters are useful synthetic intermediates particularly as the two boronic esters can be selectively functionalized. Usually, the less hindered primary boronic ester reacts, but herein, we report a coupling reaction that enables the reversal of this selectivity. This is achieved through the formation of a boronate complex with an electron‐rich aryllithium which, in the presence of an electron‐deficient aryl nitrile, leads to the formation of an electron donor–acceptor complex. Following visible‐light photoinduced electron transfer, a primary radical is generated which isomerizes to the more stable secondary radical before radical‐radical coupling with the arene radical‐anion, giving β‐aryl primary boronic ester products. The reactions proceed under catalyst‐free conditions. This method also allows stereodivergent coupling of cyclic cis‐1,2‐bis‐boronic esters to provide trans‐substituted products, complementing the selectivity observed in the Suzuki–Miyaura reaction.
Allosteric Binding‐Induced Intramolecular Mechanical‐Strain Engineering
Authors: Ma Wenxian , Cheng Tingting , Liu Fang‐Zi , Liu Yan , Yan KaKing
Published: February 2022

Recently, polymer mechanochemistry has attracted much scientific interest due to its potential to develop degradable polymers. When the two ends of a polymer chain experience a linear pulling stress, molecular strain builds up, at sufficiently strong force, a bond scission of the weakest covalent bond results. In contrast, bond‐breaking events triggered by conformational stress are much less explored. Here, we discovered that a Zn salen complex would undergo conformational switching upon allosteric complexation with alkanediammonium guests. By controlling the guest chain length, the torsional strain experienced by Zn complex can be modulated to induce bond cleavage with chemical stimulus, and reactivity trend is predicted by conformational analysis derived by DFT calculation. Such strain‐release reactivity by a Zn(salen) complex initiated by guest binding is reminiscent of conformation‐induced reactivity of enzymes to enable chemical events that are otherwise inhibited.
Care of the Patient Undergoing Robotic‐Assisted Brain Biopsy With Stereotactic Navigation: An Overview
Authors: Karasin Beth , Hardinge Tara , Eskuchen Lauren , Watkinson Johanna
Published: February 2022

Brain tumors can cause pressure, swelling, and functional changes to the surrounding tissue and lead to sensorimotor symptoms. Such tumors are either benign or malignant and their origin can be primary or metastatic. Although diagnostic studies (eg, computed tomography and magnetic resonance imaging) can reveal a mass and provide information on its location, size, and relationship to surrounding structures, the most definitive way to make a diagnosis requires a brain biopsy tissue sample. The robotic‐assisted technique with stereotactic navigation allows the neurosurgeon to merge preoperative scans with a computer program to provide a map of the planned surgical trajectory and use the robot to obtain the biopsy. The robotic‐assisted brain biopsy with navigation provides improved accuracy with small incisions that may not be possible using non–robotic‐assisted techniques. This article provides background information and an overview of the nursing considerations for patients undergoing robotic‐assisted brain biopsy procedures.
Development and properties of UV‐cured poly (propylene fumarate)/hydroxyapatite composites coatings as potential application for bone adhesive tape
Authors: Wang Liang , Chen Bing‐yu , Ji Meng‐hao , Guo Da‐gang , He Xin‐hai , Lashari Najeeb ur Rehman , Fu Chong , Zheng Jing
Published: February 2022

As an alternative for polymethyl methacrylate, poly (propylene fumarate) (PPF) has been considered as injectable and biodegradable bone cement; therefore, its mechanical and degradation properties are particularly important. As an environmentally friendly PPF‐based copolymer, which is reinforced by hydroxyapatite, was studied for the properties of the composite. The composites were investigated by evaluating their mechanical properties, hydrophilicity, in vitro degradability, and cytocompatibility. Furthermore, via applying MC3T3‐E1 cells, their cell interaction, including adhesion, proliferation, and in vitro cytotoxicity assay, were assessed. The composite reinforced with 3 wt% hydroxyapatite showed a higher lap‐shear strength (0.71 MPa) and bonding strength (5.24 MPa), a maximum compression strength at fracture (92.44 MPa), and compression strength at yield (35.44 MPa), respectively. Also, mechanical strength, hydrophilicity, and in vitro degradation of composites were enhanced in the presence of hydroxyapatite. In this condition, after a period of immersion (52 weeks) in PBS, the weight loss and degradation rate of composites were found to increased. Cell culture tests indicated that the composite was nontoxic and meaningfully facilitated cell attachment and proliferation. Accordingly, controllable strength and degradation of the composite, along with its proven biocompatibility, make the composite a candidate for the treatment of comminuted fractures.
Self‐Assembled Human Skin Equivalents Model Macrophage Activation of Cutaneous Fibrogenesis in Systemic Sclerosis
Authors: Huang Mengqi , Smith Avi , Watson Matthew , Bhandari Rajan , Baugh Lauren M. , Ivanovska Irena , Watkins Trishawna , Lang Irene , Trojanowska Maria , Black Lauren D. , Pioli Patricia A. , Garlick Jonathan , Whitfield Michael L.
Published: February 2022

Objective

The development of precision therapeutics for systemic sclerosis (SSc) has been hindered by the lack of models that accurately mimic the disease in vitro. This study was undertaken to design and test a self‐assembled skin equivalent (saSE) system that recapitulates the cross‐talk between macrophages and fibroblasts in cutaneous fibrosis.

Methods

SSc‐derived dermal fibroblasts (SScDFs) and normal dermal fibroblasts (NDFs) were cultured with CD14+ monocytes from SSc patients or healthy controls to allow de novo stroma formation. Monocyte donor–matched plasma was introduced at week 3 prior to seeding keratinocytes to produce saSE with a stratified epithelium. Tissue was characterized by immunohistochemical staining, atomic force microscopy, enzyme‐linked immunosorbent assay, and quantitative reverse transcriptase–polymerase chain reaction.

Results

Stroma synthesized de novo from NDFs and SScDFs supported a fully stratified epithelium to form saSE. A thicker and stiffer dermis was generated by saSE with SScDFs, and more interleukin‐6 and transforming growth factor β (TGFβ) was secreted by saSE with SScDFs compared to saSE with NDFs, regardless of the inclusion of monocytes. Tissue with SSc monocytes and plasma had amplified dermal thickness and stiffness relative to control tissue. Viable CD163+ macrophages were found within the stroma of saSE 5 weeks after seeding. Additionally, SSc saSE contained greater numbers of CD163+ and CD206+ macrophages compared to control saSE. TGFβ blockade inhibited stromal stiffness to a greater extent in SSc saSE compared to control saSE.

Conclusion

These data suggest reciprocal activation between macrophages and fibroblasts that increases tissue thickness and stiffness, which is dependent in part on TGFβ activation. The saSE system may serve as a platform for preclinical therapeutic testing and for molecular characterization of SSc skin pathology through recapitulation of the interactions between macrophages and fibroblasts.
Critical Role of Notch‐1 in Mechanistic Target of Rapamycin Hyperactivity and Vascular Inflammation in Patients With Takayasu Arteritis
Authors: Jiang Wanwan , Sun Mengyao , Wang Ying , Zheng Ming , Yuan Zixin , Mai Shixiong , Zhang Xin , Tang Longhai , Liu Xiyu , Wang Chunhong , Wen Zhenke
Published: February 2022

Objective

Takayasu arteritis (TA) is a major type of large vessel vasculitis characterized by progressive inflammation in vascular layers. In our recent study we identified a central role of mechanistic target of rapamycin (mTOR) hyperactivity in proinflammatory T cell differentiation in TA. This study was undertaken to explore potential mechanisms underpinning T cell–intrinsic mTOR hyperactivity and vascular inflammation in TA, with a focus on Notch‐1.

Methods

Notch‐1 expression and activity was determined according to Notch‐1, activated Notch‐1, and HES‐1 levels. We detected mTOR activity with intracellular expression of phosphorylated ribosomal protein S6. Differentiation of proinflammatory T cells was analyzed by detecting Th1 and Th17 lineage‐determining transcription factors. The function of Notch‐1 was evaluated using γ‐secretase inhibitor DAPT and gene knockdown using a short hairpin RNA (shRNA) strategy. We performed our translational study using humanized NSG mouse chimeras in which human vasculitis was induced using immune cells from TA patients.

Results

CD4+ T cells from TA patients exerted Notch‐1high, leading to mTOR hyperactivity and spontaneous maldifferentiation of Th1 cells and Th17 cells. Blockade of Notch‐1 using DAPT and Notch‐1 shRNA efficiently abrogated mTOR complex 1 (mTORC1) activation and proinflammatory T cell differentiation. Mechanistically, Notch‐1 promoted mTOR expression, interacted with mTOR, and was associated with lysosomal localization of mTOR. Accordingly, systemic administration of DAPT and CD4+ T cell–specific gene knockdown of Notch‐1 could alleviate vascular inflammation in humanized TA chimeras.

Conclusion

Expression of Notch‐1 is elevated in CD4+ T cells from TA patients, resulting in mTORC1 hyperactivity and proinflammatory T cell differentiation. Targeting Notch‐1 is a promising therapeutic strategy for the clinical management of TA.
Construction of a Nanorod Structure‐Confined Pt@CeO2 Catalyst by an In‐Situ Encapsulation Strategy for Low‐Temperature Catalytic Oxidation of Toluene
Authors: Ma Siyi , Han Weiliang , Dong Fang , Tang Zhicheng
Published: February 2022

In this work, Pt@CeO2 catalysts with a nanorod structure (Pt@CeO2−R) and a bunch structure (Pt@CeO2−B) were synthesized through an in‐situ encapsulation strategy of Pt species in Ce‐MOFs, respectively. It was discovered that the Pt@CeO2−R catalyst possessed the best catalytic performance for toluene catalytic combustion, and this result was mainly caused by the confinement of Pt nanoparticles in Ce−MOFs, which was related to the chemical state of Pt species, redox ability, and the amount of active oxygen species. The Pt@CeO2−R catalyst contained more Ce3+ species, rich Pt4+ species, and abundant active oxygen species due to the existence of the confined effect, which was conducive to promote catalytic oxidation of toluene. In addition, the Pt@CeO2−R catalyst also exhibited more redox ability, which may speed up the catalytic reaction rates. On the contrary, the Pt/CeO2−R catalyst was synthesized through a simple impregnation method and exhibited the poor activity for toluene catalytic combustion due to poor Pt4+ species and active oxygen species. Therefore, this work provides a feasible experimental basis for the study of different morphologies and encapsulated metal nanoparticles.
Health monitoring of students with autism spectrum disorder: Implementation integrity and social validation of a computer‐assisted bowel movement tracking system
Authors: Bird Frank , Shlesinger Andrew , Gopinathan Haritha , Duhanyan Kimberly , Buckley Jessica , Luiselli James K.
Published: February 2022

Many children with autism spectrum disorder (ASD) have gastrointestinal (GI) problems and associated fecal incontinence, constipation, and diarrhea. We describe the design and operation of a computer‐assisted health monitoring system for tracking and recording bowel movements at a residential school. Implementation integrity of the system by care providers was 100% for six targeted students with ASD and GI difficulties. The utility, objectives, and effectiveness of the system were rated positively by supervisory professionals, parents, and GI physicians. Our discussion focuses on the advantages of computer‐assisted data recording and instrumentation technology for documenting health measures such as bowel movement frequency and quality in children with ASD.
Effect of virtual reality guidance system on the overhaul teaching
Authors: Yang Jianwei , Liu Fu , Zhu Aihua , Wang Jinhai , Yao Dechen , Wang Xiaohui , Kou Ziming
Published: February 2022

Students' learning motivation and gains in the professional training are essential criteria for evaluating the vocational teaching level. This study designed the virtual reality guidance (VRG) system to teach the skills of urban railway vehicle overhaul. The VRG system aims to improve students' enthusiasm and gains from learning. The system has two modules, teaching and experiment modules, respectively. The teaching module added the independent design mode and evaluation mode to guide students to participate in and enjoy the teaching system actively. The experiment randomly divided 80 urban railway vehicle engineering students into the experimental and control groups. Participants underwent the entire pretest, teaching, and posttest process. The results show that the VRG system endows students with more effective operational skills learning rather than traditional teaching methods. Also, the novel system can guide students to discover their professional advantages and enhance their enthusiasm for professional learning.