bluuebunny/crossref_metadata_2025 huggingface dataset:
Highly Selective Au/ZnO via Colloidal Deposition for CO2 Hydrogenation to Methanol: Evidence of AuZn Role
Authors: Bahruji Hasliza , Almalki Mshaal , Abdullah Norli
Published: March 2021

Gold, Au nanoparticles were deposited on ZnO, Al2O3, and Ga2O3 via colloidal method in order to investigate the role of support for CO2 hydrogenation to methanol. Au/ZnO was also produced using impregnation method to investigate the effect of colloidal method to improve methanol selectivity. Au/ZnO produced via sol immobilization showed high selectivity towards methanol meanwhile impregnation method produced Au/ZnO catalyst with high selectivity towards CO. The CO2 conversion was also influenced by the amount of Au weight loading. Au nanoparticles with average diameter of 3.5 nm exhibited 4% of CO2 conversion with 72% of methanol selectivity at 250 °C and 20 bar. The formation of AuZn alloy was identified as active sites for selective CO2 hydrogenation to methanol. Segregation of Zn from ZnO to form AuZn alloy increased the number of surface oxygen vacancy for CO2 adsorption to form formate intermediates. The formate was stabilized on AuZn alloy for further hydrogenation to form methanol.  The use of Al2O3 and Ga2O3 inhibited the formation of Au alloy, and therefore reduced methanol production. Au/Al2O3 showed 77% selectivity to methane, meanwhile Au/Ga2O3 produced 100% selectivity towards CO. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).
CD133 prevents colon cancer cell death induced by serum deprivation through activation of Akt‐mediated protein synthesis and inhibition of apoptosis
Authors: Mori Yusuke , Takeuchi Ayaka , Miyagawa Kengo , Yoda Hiroyuki , Soda Hiroaki , Nabeya Yoshihiro , Watanabe Naoko , Ozaki Toshinori , Shimozato Osamu
Published: March 2021

During the early phase of tumorigenesis, primary malignant cells survive within a low nutrition environment caused by a poorly organized vascular system. Here, we sought to determine the functional significance of CD133 in the survival of cancer cells under nutrient‐poor conditions. Knockdown and overexpression experiments demonstrated that CD133 suppresses colon cancer cell death induced by serum deprivation through activation of Akt‐mediated anti‐apoptosis and protein synthesis pathways. Furthermore, serum deprivation increased the amount of endogenous CD133 protein, which was regulated at least in part by phosphoinositide 3‐kinase. Thus, it is highly likely that CD133 contributes to the acquisition/maintenance of the resistance to stress arising from nutrient deficiency in early avascular tumor tissues.
Safety and efficacy of unilateral and bilateral pallidotomy for primary dystonia
Authors: Horisawa Shiro , Fukui Atsushi , Takeda Nobuhiko , Kawamata Takakazu , Taira Takaomi
Published: March 2021

Objective

Ablation of the globus pallidus internus (pallidotomy) is an effective surgical intervention for dystonia. However, the current literature on the efficacy and safety of pallidotomy for dystonia is derived only from single‐case reports and small cohort studies.

Methods

We retrospectively analyzed patients with primary dystonia who underwent pallidotomy at our institution between 2014 and 2019. Neurological conditions were evaluated using the Burke‐Fahn‐Marsden Dystonia Rating Scale (BFMDRS, range: 0–120). We evaluated the total BFMDRS score and each subitem score (nine body regions) in the patients who underwent unilateral and bilateral pallidotomy before surgery and at last available follow‐up. Moreover, postoperative complications were analyzed.

Results

We found that 69 and 20 patients underwent unilateral and bilateral pallidotomy respectively. The mean age at dystonia onset was 40.4 ± 15.2 years. The mean clinical follow‐up period was 17.2 ± 11.6 months. Unilateral pallidotomy significantly improved the total BFMDRS score from 11.2 ± 14.7 preoperatively to 5.4 ± 7.6 at last available follow‐up (51.8% improvement, p < 0.001). Furthermore, there was a significant and independent improvement in all midline BFMDRS subitems, including eyes, mouth, speech/swallow, and neck, after unilateral pallidotomy. Bilateral pallidotomy significantly improved the total BFMDRS score from 14.6 ± 10.2 preoperatively to 3.8 ± 8.2 at last available follow‐up (74.0% improvement, p < 0.001). However, bilateral pallidotomy induced medically refractory parkinsonism (postural instability and gait disturbance) in five patients, dysarthria in three patients, and dysphagia in one patient.

Interpretation

Unilateral radiofrequency pallidotomy remains a viable treatment option for patients with some forms of dystonia. Bilateral pallidotomy cannot be recommended due to unacceptably high complication rates.
Parameter identification forWiener‐finite impulse response system with output data of missing completely at random mechanism and time delay
Authors: Jin Qibing , Wang Zeyu , Cai Wu , Zhang Yuming
Published: March 2021

In this paper, the parameter estimation issue of Wiener system with random time delay and missing output data is studied. The linear part of Wiener system is described by Finite Impulse Response (FIR) model. The mathematical formula of the Expectation Maximum algorithm to identify Wiener‐FIR system that contains the random time delay and the nonlinear output data in missing completely at random mechanism is derived, which is never considered before. To obtain the unmeasurable intermediate variable in Wiener‐FIR system, the idea of auxiliary model is adopted. The time delay and system parameters can be estimated simultaneously by this method. Numerical example and the identification of water tank system example are carried out, the effectiveness of the algorithm is proved.
Revealing the Synergy of Cation and Anion Vacancies on Improving Overall Water Splitting Kinetics
Authors: Liu Yang , Bui Huong T. D. , Jadhav Amol R. , Yang Taehun , Saqlain Shahid , Luo Yongguang , Yu Jianmin , Kumar Ashwani , Wang Hongdan , Wang Lingling , Bui Viet Q. , Kim Min Gyu , Kim Young Dok , Lee Hyoyoung
Published: March 2021

The exact understanding for each promotional role of cation and anion vacancies in bifunctional water splitting activity will assist in the development of an efficient activation strategy of inert catalysts. Herein, systematic first‐principles computations demonstrate that the synergy of anion–oxygen and cation–manganese vacancies (VO and VMn) in manganese dioxide (MnO2) nanosheets results in abnormal local lattice distortion and electronic modulation. Such alterations enrich the accessible active centers, increase conductivity, enhance the water dissociation step, and favor intermediate adsorption–desorption, consequently promoting HER and OER kinetics. As proof of concept, robust electrocatalysts, MnO2 ultrathin nanosheets doped with dual vacancies (DV–MnO2) are obtained via a maturely chemical strategy. Detailed characterizations confirm the cation vacancies‐VMn contribute to enhanced conductivity and anion vacancies‐VO enrich the active centers with optimized local electronic configurations, consistent with the simulative predictions. As expected, DV–MnO2 exhibits exceptional bifunctionality with the strong assistance of synergetic dual vacancies which act as abundant “hot spots” for active multiple intermediates. Leading to a lower cell voltage (1.55 V) in alkali electrolyte is required to reach 10 mA cm−2 for the overall water splitting system. These atomic‐level insights on synergetic DV can favor the development of activating strategy from inert electrocatalysts.
Fluid‐Dynamics‐Processed Highly Stretchable, Conductive, and Printable Graphene Inks for Real‐Time Monitoring Sweat during Stretching Exercise
Authors: Park Hong Jun , Jeong Jae‐Min , Son Seon Gyu , Kim Seo Jin , Lee Minkyung , Kim Hyo Jeong , Jeong Jihun , Hwang Sung Yeon , Park Jeyoung , Eom Youngho , Choi Bong Gill
Published: March 2021

With the development of wearable electronics, the use of engineered functional inks with printing technologies has attracted attention owing to its potential for applications in low‐cost, high‐throughput, and high‐performance devices. However, the improvement in conductivity and stretchability in the mass production of inks is still a challenge for practical use in wearable applications. Herein, a scalable and efficient fluid dynamics process that produces highly stretchable, conductive, and printable inks containing a high concentration of graphene is reported. The resulting inks, in which the uniform incorporation of exfoliated graphene flakes into a viscoelastic thermoplastic polyurethane is employed, facilitated the screen‐printing process, resulting in high conductivity and excellent electromechanical stability. The electrochemical analysis of a stretchable sodium ion sensor based on a serpentine‐structured pattern results in excellent electrochemical sensing performance even under strong fatigue tests performed by repeated stretching (300% strain) and release cycles. To demonstrate the practical use of the proposed stretchable conductor, on‐body tests are carried out in real‐time to monitor the sweat produced by a volunteer during simultaneous physical stretching and stationary cycling. These functional graphene inks have attractive performance and offer exciting potential for a wide range of flexible and wearable electronic applications.
High‐Throughput One‐Photon Excitation Pathway in 0D/3D Heterojunctions for Visible‐Light Driven Hydrogen Evolution
Authors: Li Bo , Peng Wei , Zhang Jing , Lian Ji‐Chun , Huang Tao , Cheng Na , Luo Ziyu , Huang Wei‐Qing , Hu Wangyu , Pan Anlian , Jiang Lang , Huang Gui‐Fang
Published: March 2021

The development of an effective one‐photon excitation pathway to improve the charge‐carrier separation and mobility of semiconductors, which have been proven to be favorable for heterogeneous catalysis, is highly desirable but remains a great challenge. Herein, a high‐throughput one‐photon excitation pathway is reported by constructing 0D carbon dots/3D porous carbon nitride nanovesicles (denoted as CDs/PCN NVs) heterostructures for photocatalytic hydrogen evolution. In particular, the optimum CDs/PCN NVs heterostructures exhibit an impressive performance of 14.022 mmol h−1 g−1, which is 56.54 times higher than that of pristine CN. Detailed characterization reveals that the improved performance is primarily attributed to the high‐throughput and one‐photon excitation pathway. The former could be attributed to a great deal of CDs with high charge‐carrier mobility coupled to PCN NVs, which enable more electrons to be photoexcited via the broad absorption response, and the multiple reflection of incident light owing to the porous nanovesicle structure with shortened route of carriers migrating toward the surface; the latter would lead to the photoinduced holes and electrons accumulated at the valence band of PCN NVs and surface of CDs, respectively, achieving an effective spatial separation. The high‐throughput one‐photon excitation pathway demonstrated here may provide insights into the development of nanocomposites for various related applications.
Biomineralization Directed by Prenucleated Calcium and Phosphorus Nanoclusters Improving Mechanical Properties and Osteogenic Potential of Antheraea pernyi Silk Fibroin‐Based Artificial Periosteum
Authors: Shuai Yajun , Lu Huan , Lv Ruyin , Wang Jie , Wan Quan , Mao Chuanbin , Yang Mingying
Published: March 2021

The use of biomacromolecules as templates to control the nucleation and growth of hydroxyapatite crystals to prepare bioactive materials is a valuable approach in bone tissue engineering. Here, an artificial periosteum is prepared by biomineralizing Antheraea pernyi fibroin (AF) membrane with prenucleated nanoclusters, which can promote the osteogenic differentiation of mesenchymal stem cells (MSCs) and induce the formation of bone matrix protein in vivo. To achieve this, a biologically inspired prenucleated calcium and phosphorus nanocluster mineralization system is designed to nucleate and generate hydroxyapatite crystals on the surface of the AF membrane. This biomineralization process provides AF membranes with improved elastic modulus and tensile strength. Subsequently, cell viability assay, hemolysis test, and H&E staining show that the mineralized AF (MAF) membranes has good cytocompatibility, hemocompatibility, and histocompatibility in vitro and in vivo. Additionally, the MAF membranes significantly promote osteogenic differentiation of MSCs in the absence of osteogenic inducer in vitro. Experiments in vivo demonstrate that bone‐related matrix proteins are highly expressed in MAF groups with or without MSCs seeded. Therefore, the use of bioinspired prenucleated nanoclusters to prepare artificial periosteum based on biomineralized AF membrane is a promising strategy in the field of bone tissue engineering.
Programmable Design and Performance of Modular Magnetic Microswimmers
Authors: Pauer Christoph , du Roure Olivia , Heuvingh Julien , Liedl Tim , Tavacoli Joe
Published: March 2021

Synthetic biomimetic microswimmers are promising agents for in vivo healthcare and important frameworks to advance the understanding of locomotion strategies and collective motion at the microscopic scale. Nevertheless, constructing these devices with design flexibility and in large numbers remains a challenge. Here, a step toward meeting this challenge is taken by assembling such swimmers via the programmed shape and arrangement of superparamagnetic micromodules. The method's capacity for design flexibility is demonstrated through the assembly of a variety of swimmer architectures. On their actuation, strokes characterized by a balance of viscous and magnetic forces are found in all cases, but swimmers formed from a series of size‐graded triangular modules swim quicker than more traditional designs comprising a circular “head” and a slender tail. Linking performance to design, rules are extracted informing the construction of a second‐generation swimmer with a short tail and an elongated head optimized for speed. Its fast locomotion is attributed to a stroke that better breaks beating symmetry and an ability to beat fully with flex at high frequencies. Finally, production at scale is demonstrated through the assembly and swimming of a flock of the triangle‐based architectures to reveal four types of swimmer couplings.
Porous Ionic Liquids: Structure, Stability, and Gas Absorption Mechanisms
Authors: Avila Jocasta , Červinka Ctirad , Dugas Pierre‐Yves , Pádua Agílio A. H. , Costa Gomes Margarida
Published: March 2021

Porous ionic liquids prepared from phosphonium‐based ionic liquids and metal‐organic frameworks (MOFs) are fluid in large ranges of temperature including ambient. It is shown that the ion pairs are too voluminous to enter the pores of the MOF, so the porous liquids remain several months as suspensions with permanent free volume, capable of absorbing large quantities of gases. The increase in gas absorption, when compared with the pure ionic liquids, is proportional to the amount of porous solid in suspension. Structural features of the MOFs and of the ionic liquids are maintained in the suspensions. Thermodynamic analysis and molecular simulations show that the driving force for gas absorption by the porous ionic liquids is energetic as well as structural being controlled by gas‐solid affinity or by the porous liquid free volume. The enthalpy of gas absorption allows easy regeneration of the porous liquid in all cases. The dissolved gases fluidify the porous ionic liquids, different gases having distinct effects on mass transport. The molecular mechanisms that explain the stability of the suspensions and their capacity for gas absorption are identified and point toward easy design rules that will enable numerous applications of these innovative materials as reaction or separation media.
Food Sensors: Challenges and Opportunities
Authors: Weston Max , Geng Shu , Chandrawati Rona
Published: March 2021

Food sensors have been developed for quality monitoring and contaminant detection to improve food management. Despite the alarming rates of food waste and food‐related illness, few food sensor technologies are utilized and translated into commercial products. This review aims to explore challenges and opportunities relating to sensor translation by first documenting recent advances in state‐of‐the‐art optical and electronic food sensors that target common analytes including temperature, humidity, pH, gases, pesticides, and pathogens. Promising sensors are designed with careful consideration of the chemistry of the contaminant or quality marker which they detect and the inherent challenges of analyte recognition in complex food samples. Recent advances focus on the incorporation of sensors into materials and devices for food packaging and processing. Challenges and opportunities for food sensor translation are then identified and discussed including the complexity of and natural variation in food products, different causes of food spoilage, the food–sensor interface, signal processing and governing legislation. For the successful translation of sensors into ubiquitous features on food products, these issues must be addressed through material and design advances.
2D Layered Materials for Ultraviolet Photodetection: A Review
Authors: Kaushik Shuchi , Singh Rajendra
Published: March 2021

2D layered materials (2DLMs) have revolutionized the field of optoelectronics owing to their exceptional properties of strong light–matter interaction, atomic‐level thickness, flexibility, and ability to form van der Waals heterostructures. Most of the research in this area is based on narrow bandgap materials such as transition metal dichalcogenides, which are ideal for fabricating visible and infrared photodetectors. However, utilizing the benefits of 2D materials for the detection of ultraviolet light requires focus on newly emerging wide bandgap 2DLMs. In the present review, an attempt is made to highlight the significance of wide bandgap 2DLMs for fabricating state‐of‐the‐art ultraviolet photodetectors. In this review, first, the fundamentals of photodetectors, including various sensing mechanisms, are discussed. After describing the growth techniques briefly, the readers are introduced to the role of 2DLMs in ultraviolet photodetection based on their bandgap distribution. This is followed by a comprehensive review of the structure, properties and ultraviolet photodetectors based on various 2DLM families including main group metal chalcogenides (GaS, GaSe, GeS2), metal oxides (MoO3), metal halides (PbI2), metal phosphorus trichalcogenides (NiPS3, MnPS3) and hexagonal boron nitride (h‐BN). Finally, the review is summarized and the authors’ perspective is given on the challenges and upcoming development in this field.
2D Materials Enabled Next‐Generation Integrated Optoelectronics: from Fabrication to Applications
Authors: Cheng Zhao , Cao Rui , Wei Kangkang , Yao Yuhan , Liu Xinyu , Kang Jianlong , Dong Jianji , Shi Zhe , Zhang Han , Zhang Xinliang
Published: March 2021

2D materials, such as graphene, black phosphorous and transition metal dichalcogenides, have gained persistent attention in the past few years thanks to their unique properties for optoelectronics. More importantly, introducing 2D materials into silicon photonic devices will greatly promote the performance of optoelectronic devices, including improvement of response speed, reduction of energy consumption, and simplification of fabrication process. Moreover, 2D materials meet the requirements of complementary metal‐oxide‐semiconductor compatible silicon photonic manufacturing. A comprehensive overview and evaluation of state‐of‐the‐art 2D photonic integrated devices for telecommunication applications is provided, including light sources, optical modulators, and photodetectors. Optimized by unique structures such as photonic crystal waveguide, slot waveguide, and microring resonator, these 2D material‐based photonic devices can be further improved in light‐matter interactions, providing a powerful design for silicon photonic integrated circuits.
Dual Inhibition of DKC1 and MEK1/2 Synergistically Restrains the Growth of Colorectal Cancer Cells
Authors: Kan Guangyan , Wang Ziyang , Sheng Chunjie , Chen Gong , Yao Chen , Mao Yizhi , Chen Shuai
Published: March 2021

Colorectal cancer, one of the most commonly diagnosed cancers worldwide, is often accompanied by uncontrolled proliferation of tumor cells. Dyskerin pseudouridine synthase 1 (DKC1), screened using the genome‐wide RNAi strategy, is a previously unidentified key regulator that promotes colorectal cancer cell proliferation. Enforced expression of DKC1, but not its catalytically inactive mutant D125A, accelerates cell growth in vitro and in vivo. DKC1 knockdown or its inhibitor pyrazofurin attenuates cell proliferation. Proteomics, RNA immunoprecipitation (RIP)‐seq, and RNA decay analyses reveal that DKC1 binds to and stabilizes the mRNA of several ribosomal proteins (RPs), including RPL10A, RPL22L1, RPL34, and RPS3. DKC1 depletion significantly accelerates mRNA decay of these RPs, which mediates the oncogenic function of DKC1. Interestingly, these DKC1‐regulated RPs also interact with HRAS and suppress the RAS/RAF/MEK/ERK pathway. Pyrazofurin and trametinib combination synergistically restrains colorectal cancer cell growth in vitro and in vivo. Furthermore, DKC1 is markedly upregulated in colorectal cancer tissues compared to adjacent normal tissues. Colorectal cancer patients with higher DKC1 expression has consistently poorer overall survival and progression‐free survival outcomes. Taken together, these data suggest that DKC1 is an essential gene and candidate therapeutic target for colorectal cancer.
Thermomechanical Manipulation of Electric Transport in MoTe2
Authors: Kim Dohyun , Lee Jun‐Ho , Kang Kyungrok , Won Dongyeun , Kwon Min , Cho Suyeon , Son Young‐Woo , Yang Heejun
Published: March 2021

Layered semimetals such as monoclinic MoTe2 and WTe2 demonstrate superconducting, topological insulating, and Weyl semimetallic states based on their unique electronic band topology. While doping concentration, lattice constants, and spin–orbit coupling can largely modulate the quantum states of the semimetals, a puzzling issue is that their functional carrier density and magnetoresistance for practical applications critically vary by temperature, which cannot be explained by the conventional phonon effect or a structural phase transition. Here, a native doping‐mediated thermomechanical manipulation of electric transport in semimetallic MoTe2 is reported, where effective transport is controlled by temperature in an equivalent manner to electric gating. Combining X‐ray diffraction, scanning tunneling microscopy, transport measurements, and first‐principles calculations, a Fermi level shift and subsequent changes in electronic structures are revealed as the origins of the practical transport changes in MoTe2. Moreover, the initial doping state of the MoTe2, determined by the Te vacancy density in two different growth methods, reciprocally affects the thermomechanical lattice and band structure changes, which is promising for novel electronic applications such as magnetic sensors and memory devices with layered semimetals.
Boosting the Performance of Liquid‐Gated Nanotransistor Biosensors Using Single‐Trap Phenomena
Authors: Kutovyi Yurii , Piatnytsia Volodymyr , Boichuk Nazarii , Zadorozhnyi Ihor , Li Jie , Petrychuk Mykhailo , Vitusevich Svetlana
Published: March 2021

In small‐area transistors, the trapping/detrapping of charge carriers to/from a single trap located in the gate oxide near the Si/SiO2 interface leads to the discrete switching of the transistor drain current, known as single‐trap phenomena (STP), resulting in random telegraph signals. Utilizing the STP‐approach, liquid‐gated (LG) nanowire (NW) field‐effect transistor biosensors have recently been proposed for ultimate biosensing with enhanced sensitivity. In this study, the impact of channel doping concentration on the capture process of charge carriers by a single trap in LG silicon NW structures is investigated. A significant effect of the channel doping concentration on the single‐trap dynamic is revealed. To understand the mechanism behind unusual capture time behavior compared to that predicted by the classical Shockley–Read–Hall theory, an analytical model based on the rigorous description of the additional energy barrier that charge carriers have to overcome to be captured by the trap at different gate voltages is developed. The enhancement of the sensitivity for single‐trap phenomena biosensing with an increase of the channel doping concentration is explained within the framework of the proposed analytical model. The results open prospects for the development of advanced single trap‐based devices.
Light‐Regulated Mott Transition for On‐Demand Multilevel Memory Storage, Processing, and Energy Efficient Machine Vision
Authors: Kumar Mohit , Pawase Chaitali Jagannath , Choi Hyobin , Kim Sangwan , Seo Hyungtak
Published: March 2021

Photosensing, data processing, and sequential memory storage are indispensable components for advanced optoelectronic devices. Nevertheless, despite enormous independent research efforts, achieving well‐controlled cofunctionality such as sensing, processing, and manifold memory storage within a single unit remain a critical issue. Here, a Mott‐insulator‐based monolithic photosensor that, depending on illuminating intensity and applied bias, can simultaneously store tunable multilevel data without latency is demonstrated. In particular, the threshold voltage to initiate the insulator‐to‐metal transition has been regulated from 4.5 to 1.5 V by changing the photon illumination intensity from dark to 6 mW cm−2. Microscopic evidence of Mott transition at the nanoscale is revealed through current maps obtained using conductive atomic force microscopy. Further, as a front‐end image sensor, the authors’ device offers on‐demand photo‐intensity sensing and edge detection with direct optical input, which is confirmed by simulation. This study intends an essential breakthrough toward on‐demand photosensing, data storage, and processing even at nanoscale, and offers the opportunity to utilize it for various applications including in volatile memory storage, neuromorphic cameras, and emergency alert systems.
Thickness and Spin Dependence of Raman Modes in Magnetic Layered Fe3GeTe2
Authors: Kong Xiangru , Berlijn Tom , Liang Liangbo
Published: March 2021

2D layered Fe3GeTe2 has attracted increasing attention due to its high magnetic ordering temperature and novel physical properties. Lattice dynamics is a fundamental property of Fe3GeTe2, and its relationships with the number of layers and interlayer spin ordering have not yet been explored in depth. Here, by first‐principles density functional theory calculations, the phonon vibrations and Raman intensities of Fe3GeTe2 are systematically studied from the bulk to monolayer structures. Furthermore, the spin‐phonon coupling effect is investigated by considering different interlayer magnetic orderings: ferromagnetic and antiferromagnetic. It is found that the frequencies of Raman modes in Fe3GeTe2 exhibit considerable dependence on the layer number and spin ordering. The results not only reveal the notable spin‐phonon interactions in Fe3GeTe2, but also demonstrate that Raman modes can be utilized for characterizing the sample thickness and interlayer spin ordering in this 2D magnet.
Quantum Transport in Monolayer α‐CS Field‐Effect Transistors
Authors: Guo Shiying , Zhou Wenhan , Qu Hengze , Zhang Shengli , Liu Wenqiang , Liu Gaoyu , Xia Xinyan , Song Xiufeng , Zeng Haibo
Published: March 2021

2D puckered materials similar to black phosphorene (BP) have tunable electronic structures, high mobility, and anisotropy, and are expected to become possible candidate channels for post‐silicon field‐effect transistors (FETs). Herein, monolayer α‐CS with puckered structure is evaluated as a promising channel material for sub‐5 nm FETs by using first principle quantum transport simulation. Monolayer α‐CS FETs can satisfy the requirements of the International Technology Roadmap for Semiconductors (ITRS) for high‐performance (HP) and low‐power (LP) applications. The on‐state current can reach 3700 µA µm−1 for HP FET at 5 nm channel length and the on‐off ratio of LP FET is exceeding 107, both superior to those of other 2D channels like BP and InSe. The results suggest that α‐CS as a competitive channel material opens a new avenue for the future electronic technology in the upcoming Internet of Things.
Metal‐Textile Laser Welding for Wearable Sensors Applications
Authors: Fromme Nicolas P. , Li Yifan , Camenzind Martin , Toncelli Claudio , Rossi René M.
Published: March 2021

Electronic textile (E‐textile), an emerging technology, has the potential to revolutionize consumer electronics by transforming them into wearable devices. Highly conductive, textile conductors, suitable for commercialization, have yet not been developed. Here, a new metal‐textile laser welding method is presented for a rapid one‐step, stable, and cost‐efficient manufacturing of electrically conductive textiles. This method is a direct on‐textile approach for customized 2D nanothick metal coatings with flexible design. Different metals, like palladium, silver, or copper can be welded on functional membranes and textiles containing polymers. As shown by bonding a copper 2D pattern on a polyamide textile, the resistivity does not vary if compared to the bulk material. The generated interlocking bonding ensures strong physical adhesion between the partly molten polyamide fibers and a copper layer, resisting up to 10 000 abrasion cycles using the standardized Martindale test and up to 42 000 flexion cycles using the industrial standardized Schildknecht test. A promising application for textile integrated conductors is body monitoring sensors. The feasibility of a laser welded resistance temperature sensors on a functional membrane is demonstrated without impairing its mechanical stability. This technology presents suitable properties and variabilities for a wide range of application in E‐textiles and its commercialization.
Computationally Guided Synthesis of High Performance Thermoelectric Materials: Defect Engineering in AgGaTe2
Authors: Zhong Yaqiong , Sarker Debalaya , Fan Tao , Xu Liangliang , Li Xie , Qin Guang‐Zhao , Han Zhong‐Kang , Cui Jiaolin
Published: March 2021

The rational synthesis of high‐performance thermoelectric (TE) materials guided by theoretical design is still in its infancy. Here by computationally exploiting the possibilities of materials’ dopability and hence the electron–phonon transport/scattering, a new defective compound, AgGaTe2, with simultaneous Ag deficiency and isoelectronic substitution of In on Ga‐site (InGa) is predicted, and its high performance is then confirmed via experiments. Using density functional theory and density functional perturbation theory calculations, it is identified that controlled defects viz. Ag vacancy and In substitution in AgGaTe2 system can lead to extremely low lattice thermal conductivity (κL) of around 0.13 WK−1 m−1 at 850 K. This ultralow κL results from both the Ag vacancy that serves as a better rattler and the extra phonon scattering due to the defect induced internal lattice distortion (ψ). The synthesized compounds Ag0.85Ga1−xInxTe2 (x = 0–0.3) indeed achieve the extremely low κL (0.08 WK−1 m−1 for x = 0.15). As a result, the highest TE figure of merit (ZT) of 1.44 is obtained, which is the highest recorded value for silver‐based ternary chalcopyrite semiconductors to date.
Enhanced Selective Charge Collection with Metal–Insulator–Semiconductor Junction in Electron Transport Layer‐Free Perovskite Solar Cells
Authors: Huang Like , Zhu Yuejin
Published: March 2021

Electron transport layer (ETL)‐free perovskite solar cells (PSCs) have witnessed great progress via material and interface engineering. Enlighten by the wisdom from an old story of efficient silicon solar cells design, highly efficient MINP (metal/insulator/n‐type perovskite/p‐type spiro‐MeOTAD) PSC with polar insulating inter‐layer (PIIL) modified fluorine‐doped tin oxide (FTO) is reported as electron selective contact. The PIIL forms metal‐insulator‐semiconductor (MIS) junction with FTO and perovskite layer, while the n‐type perovskite forms P‐N junction with p‐type spiro‐MeOTAD. Unlike the classic MINP silicon solar cells where the I‐layer is usually neutral tunneling layer, the PIIL here optimizes the energy level alignment at the FTO/perovskite interface with its intrinsic electronic polarity while acting as an effective tunneling layer. Also, the functional group of the PIIL passivates the FTO/perovskite interface defects thus suppressing carrier recombination thereof and enhancing all device performance parameters simultaneously. Accordingly, the power conversion efficiency is greatly improved from 12.82% to 19.75%. With the enhanced electron collection and decreased carrier recombination of the MIS junction, this collaborative effect of interface engineering and defect passivation contribute to more stable ETL‐free PSC with less hysteresis. This work highlights the potential of novel device and interface design for simple‐structured, efficient and cost‐effective PSCs.
Tailoring Slurries Using Cosolvents and Li Salt Targeting Practical All‐Solid‐State Batteries Employing Sulfide Solid Electrolytes
Authors: Kim Kyu Tae , Oh Dae Yang , Jun Seunggoo , Song Yong Bae , Kwon Tae Young , Han Yoonjae , Jung Yoon Seok
Published: March 2021

Polymeric binders that can undergo slurry fabrication and minimize the disruption of interfacial Li+ contact are imperative for sheet‐type electrodes and solid electrolyte films in practical all‐solid‐state Li batteries (ASLBs). Although dry polymer electrolytes (DPEs) are a plausible alternative, their use is complicated by the severe reactivity of sulfide solid electrolytes and the need to dissolve Li salts. In this study, a new scalable fabrication protocol for a Li+‐conductive DPE‐type binder, nitrile‐butadiene rubber (NBR)‐LiTFSI, is reported. The less‐polar dibromomethane and more‐polar hexyl butyrate in cosolvents work synergistically to dissolve NBR and LiTFSI, while preserving Li6PS5Cl0.5Br0.5. It is found that the dispersion of NBR can be controlled by the fraction of the antisolvent (hexyl butyrate), which in turn affects the corresponding performance of the ASLBs. Sheet‐type LiNi0.70Co0.15Mn0.15O2 electrodes tailored using NBR‐LiTFSI outperform those prepared using the conventional insulating binder (NBR) in terms of capacity (163 vs 147 mA h g−1) and initial Coulombic efficiency (78.9 vs 70.4%), which is attributed to the facilitated interfacial Li+ transport, as confirmed by 6Li nuclear magnetic resonance and electrochemical measurements. Moreover, NBR‐LiTFSI is functional at 70 °C and in a graphite anode. Finally, the promising performance of pouch‐type LiNi0.70Co0.15Mn0.15O2/graphite ASLBs is also demonstrated.
Design and operational considerations of catalytic membrane reactors for ammonia synthesis
Authors: Zhang Zhenyu , Way J. Douglas , Wolden Colin A.
Published: March 2021

Production of ammonia using hydrogen derived from renewable electricity instead of hydrocarbon reforming would dramatically reduce the carbon footprint of this commodity chemical. Novel technologies such as catalytic membrane reactors (CMRs) may potentially be more compatible with distributed ammonia production than the conventional Haber–Bosch process. A reactor model is developed based on integrating a standard industrial iron catalyst into a CMR equipped with an inorganic membrane that is selective to NH3 over N2/H2. CMR performance is studied as functions of wide ranges of membrane properties and operating conditions. Conversion and ammonia recovery are dictated principally by the ammonia permeance, and the benefits by using membranes become significant above 100 GPU = 3.4 × 10−8 mol m−2 s−1 Pa−1. To be effective, the CMR requires a minimum selectivity for ammonia of 10 over both nitrogen and hydrogen and purity scales with the effective selectivity. Increasing the pressure of operation significantly improves all metrics, and at P = 30 bar with a quality membrane, ammonia is almost completely recovered, enabling direct recycle of unreacted hydrogen and nitrogen without need for recompression. Temperature drives conversion and scales monotonically without thermodynamic limitations in a CMR. Alternatively, the temperature may be reduced as low as 300°C while achieving conversion levels surpassing equilibrium limits at T = 400°C in a conventional reactor.
How Sense of Community Affects Sense of Self Among Sexual Minorities: Critical Consciousness as a Mediating Mechanism
Authors: Yip Charles Chiu Hung , Chan Kevin Ka Shing
Published: March 2021

Research shows that sense of community may enable lesbian, gay, and bisexual (LGB) individuals to resist and fight against societal heterosexism and increase their positive sense of self. Less is known, however, about the underlying processes. The present study examined whether sense of community would affect sense of self (i.e., identity affirmation and self‐esteem) through critical consciousness (i.e., critical reflection and critical action) among LGB individuals. A total of 401 LGB individuals from Hong Kong, China, provided cross‐sectional questionnaire data on sense of community, critical reflection, critical action, identity affirmation, and self‐esteem. Structural equation modeling and bootstrap analyses were performed to analyze the direct and indirect relations among the variables. Results showed that sense of community was positively associated with critical action, and this association was mediated by critical reflection. Moreover, critical action was positively associated with self‐esteem, and this association was mediated by identity affirmation. Theoretically, this study demonstrated how LGB individuals’ sense of community may have a positive impact on their sense of self through the mechanism of critical consciousness. Practically, this study pointed to the utility of cultivating positive in‐group perceptions among LGB individuals in liberating them from oppressive ideology, mobilizing them to resist social injustice, enhancing their identity affirmation, and increasing their self‐esteem.
“Why is it that all the Dangerous Children are Black From the Neighborhoods?”: Critical Phenomenology of the Concept of Risk Among Adults Educated at Therapeutic Boarding Schools
Authors: Frantsman‐Spector Alin , Shoshana Avihu
Published: March 2021

This article is based on in‐depth interviews with Israeli adults who had been labeled in their childhood as being at risk and removed from their home to residential care settings (RCS) by court order due to their families' extreme poverty. In seeking their perspective, the present article addresses the pivotal question of how, as adults, they define, experience, and relate to the concept of “at‐risk children.” The interviews revealed critical phenomenological readings of the notion of risk and the social institution of RCS. Analyzing the critical phenomenology of the interviewees offers research contributions concerning the study of the social construction of the concept of risk, its phenomenology, and the long‐term ramifications of labeling children as being at risk and of educating them in RCS.
Leukocyte telomere length is inversely associated with a metabolic risk score in Mesoamerican children
Authors: Garfein Joshua , Flannagan Kerry S. , Rittman Danielle , Ramirez‐Zea Manuel , Villamor Eduardo ,   For the Nine Mesoamerican Countries Metabolic Syndrome Study (NiMeCoMeS) Group
Published: March 2021

Objective

Leukocyte telomere length (LTL) may be involved in the etiology of the metabolic syndrome (MetS). We examined the associations of LTL with MetS and its components among Mesoamerican children and their adult parents, in a region where MetS prevalence is high.

Methods

We conducted a cross‐sectional study of 151 children aged 7–12 years and 346 parents from the capitals of Belize, Honduras, Nicaragua, Costa Rica, Panama, and Chiapas State, Mexico. We quantified LTL by qPCR on DNA extracted from whole blood. In children, we created an age‐ and sex‐standardized metabolic risk score using waist circumference (WC), the homeostasis model of insulin resistance (HOMA‐IR), blood pressure, serum high‐density lipoprotein (HDL) cholesterol, and serum triglycerides. In adults, MetS was defined according to the National Cholesterol Education Program's Adult Treatment Panel III definition. We estimated mean differences in metabolic risk score and prevalence ratios of MetS across quartiles of LTL using multivariable‐adjusted linear and Poisson regression models, respectively.

Results

In children, every 1 LTL z‐score was related to an adjusted 0.05 units lower (95% CI: −0.09, −0.02, P = 0.005) MetS risk score, through WC, HOMA‐IR, and HDL. Among adults, LTL was not associated with MetS prevalence; however, every 1 LTL z‐score was associated with an adjusted 34% lower prevalence of high fasting glucose (95% CI: 3%, 55%, p = .03).

Conclusions

Among Mesoamerican children, LTL is associated with an improved metabolic profile; among adults, LTL is inversely associated with the prevalence of high fasting glucose.
Zwitterion‐Catalyzed Amino‐Dibromination of Nitroalkenes: Scope, Mechanism, and Application to The Synthesis of Glycinamides
Authors: Ng Wing‐Hin , Lam Ying‐Pong , Hu Rong‐Bin , Ng Wing‐Lok , Yeung Ying‐Yeung
Published: March 2021

Glycinamides are valuable building blocks of natural products and biological relevant molecules. Many existing methods for the synthesis of glycinamides rely on harsh conditions. Herein, we report a zwitterion‐catalyzed aminobromination of nitroalkenes using N‐bromosuccinimide as the Br source and the amide donor. The resulting aminobromide products are converted into glycinamides.
N‐Nitroso As A Novel Directing Group in Transition‐Metal‐Catalyzed C(sp2)−H Bond Functionalizations of N‐Nitrosoanilines
Authors: De Saroj Ranjan
Published: March 2021

In the last few decades, the syntheses of bioactive natural products and functional materials have been achieved via C−H bond functionalizations where the transition metals in coordination with the directing groups trigger the C−H bond activation. A wide variety of directing groups has been recognized for transition‐metal‐catalyzed ortho‐C−H bond functionalization of arenes. Recently, N‐nitroso group has been established as a new, efficient and sometimes as a traceless directing group in ortho‐C(sp2)−H bond functionalizations of N‐nitrosoanilines. During functioning as a traceless‐directing‐group, the N ‐O bond of N‐nitrosoaniline acts as an internal oxidant to recycle the employed catalyst. Pd, Rh, Co, Ru and Ir catalysts have been screened for the ortho C−H bond functionalizations of N‐nitrosoanilines constructing new C−C, C−O, C−N and C−X bonds. Herein, we have summarized all the recently developed N‐nitroso group directed ortho‐C(sp2)−H bond functionalization reactions of N‐nitrosoanilines.
carba‐Nicotinamid‐Adenin‐Dinukleotid‐Phosphat: Robuster Cofaktor für die Redox‐Biokatalyse
Authors: Zachos Ioannis , Döring Manuel , Tafertshofer Georg , Simon Robert C. , Sieber Volker
Published: March 2021

Hier berichten wir über ein neues robustes Nicotinamid‐Dinukleotidphosphat‐Cofaktor‐Analogon (carba‐NADP+) und dessen Akzeptanz von zahlreichen Enzymen aus der Klasse der Oxidoreduktasen. Es wurde festgestellt, dass das Ersetzen eines Ribose‐Sauerstoffs durch eine Methylengruppe des natürlichen NADP+ die Stabilität drastisch erhöht. Zersetzungsexperimente bei moderaten und hohen Temperaturen mit den Cofaktoren zeigten eine drastische Erhöhung der Halbwertszeit bei erhöhten Temperaturen, da die Hydrolyse der Pyridinium‐N‐Glykosid‐Bindung deutlich reduziert wird. Insgesamt wurden mehr als 27 verschiedene Enzyme erfolgreich getestet, von denen einige im Detail vergleichend charakterisiert wurden. Der Cofaktor carba‐NADP+ eröffnet das Feld der Redox‐Biokatalyse unter extremen Bedingungen.
Prodrug Activation by Gold Artificial Metalloenzyme‐Catalyzed Synthesis of Phenanthridinium Derivatives via Hydroamination
Authors: Chang Tsung‐Che , Vong Kenward , Yamamoto Tomoya , Tanaka Katsunori
Published: March 2021

An emerging approach in the field of targeted drug delivery is the establishment of abiotic metal‐triggered prodrug mechanisms that can control the release of bioactive drugs. Currently, the design of prodrugs that use abiotic metals as a trigger relies heavily on uncaging strategies. Here, we introduce a strategy based on the gold‐catalyzed activation of a phenanthridinium‐based prodrug via hydroamination under physiological conditions. To make the prodrug strategy biocompatible, a gold artificial metalloenzyme (ArM) based on human serum albumin, rather than the free gold metal complex, was used as a trigger for prodrug activation. The albumin‐based gold ArM protected the catalytic activity of the bound gold metal even in the presence of up to 1 mM glutathione in vitro. The drug synthesized via the gold ArM exerted a therapeutic effect in cell‐based assays, highlighting the potential usefulness of the gold ArM in anticancer applications.
Direct Activation of a Remote C(sp3)–H Bond Enabled by a Visible‐Light Photosensitized Allene Moiety
Authors: Liu Jiaxin , Wei Yin , Shi Min
Published: March 2021

Despite allene derivatives have been always regarded as a radical accepter in traditional radical chemistry for decades, the reactivity of allene derivatives under excited state in radical chemistry was rarely explored. Herein, we wish to report an example to engage triplet‐excited state of allene moiety as hydrogen‐atom‐transfer (HAT) partner in the activation of remote sp3 C−H bond via visible‐light irradiation under mild reaction conditions with broad substrate scope and good functional‐group tolerance. The reaction mechanism involving the generation of triplet excited state of allene derivative and the subsequent HAT process was supported by deuterium labeling, kinetic analysis experiments and DFT calculations.
Design of Multi‐Shelled Hollow Cr2O3Spheres for Metabolic Fingerprinting
Authors: Li Rongxin , Zhou Yongjie , Liu Chao , Pei Congcong , Shu Weikang , Zhang Chaoqi , Liu Lianzhong , Zhou Liang , Wan Jingjing
Published: March 2021

Schizophrenia (SZ) detection enables effective treatment to improve the clinical outcome, but objective and reliable SZ diagnostics are still limited. An ideal diagnosis of SZ suited for robust clinical screening must address detection throughput, low invasiveness, and diagnosis accuracy. Herein, we built a multi‐shelled hollow Cr2O3spheres (MHCSs) assisted laser desorption/ionization mass spectrometry (LDI MS) platform for the direct metabolic profiling of biofluids towards SZ diagnostics. The MHCSs displayed strong light absorption for enhanced ionization and microscale surface roughness with stability for the effective LDI of metabolites. We profiled urine and serum metabolites (≈1 μL) with the enhanced LDI efficacy in seconds. We discriminated SZ patients (SZs) from healthy controls (HCs) with the highest area under the curve (AUC) value of 1.000 for the blind test. We identified four compounds with optimal diagnostic power as a simplified metabolite panel for SZ and demonstrated the metabolite quantification for clinic use. Our approach accelerates the growth of new platforms toward a precision diagnosis in the near future.