bluuebunny/crossref_metadata_2025 huggingface dataset:
A Tumor‐Specific Platform of Peroxynitrite Triggering Ferroptosis of Cancer Cells
Authors: Huang Daipeng , Huang Haiqiao , Li Mingle , Fan Jiangli , Sun Wen , Du Jianjun , Long Saran , Peng Xiaojun
Published: October 2022

Peroxynitrite (ONOO−) is a potent oxidant and nucleophile participating in a variety of pathophysiological processes as well as playing a major role in cancer therapy. However, the intracellular environment of solid tumors severely restricts the production of ONOO−, which leads to an unsatisfactory anticancer effect. Here, a tumor‐specific platform for ONOO− generation, prepared by linking a type I photosensitizer with a GSH‐responsive NO donor, is constructed to overcome the tumor hypoxic microenvironment and enhance treatment efficiency (NBS‐2S‐NO). Responding to the overexpressed glutathione (GSH) within tumors, NBS‐2S‐NO can selectively induce ONOO− generation after a cascade including red light irradiation causing superoxide radical (O2•−) production, GSH‐triggered NO release, and fast reaction between O2•− and NO. The generated ONOO− can cause oxidative damage to tumor cells, induce lipid peroxidation (LPO) during the cell death process and finally cause ferroptosis. Both in vitro and in vivo outcomes demonstrate the notable anticancer ferroptosis efficacy of this platform, suggesting not only an effective ferroptosis strategy for the design of new photosensitizers but also a worthy of reference for antioxidant regulation to enhance the oxidative damage during the tumor treatment process.
2D Transition Metal Dichalcogenides‐Based Electrocatalysts for Hydrogen Evolution Reaction
Authors: Mondal Aniruddha , Vomiero Alberto
Published: October 2022

Hydrogen is an efficient, clean, and economical energy source, owing to its huge energy density. Electrochemical water splitting is a potential candidate for inexpensive and eco‐friendly hydrogen production. Recently, the development of 2D transition metal chalcogenides (TMDs) nanomaterials with a variety of physicochemical properties has shown their potential as eminent non‐noble metal‐based nanoscale electrocatalysts for hydrogen evolution. Nanostructuring such materials induces deep modification of their functionalities, compared to their bulk counterparts. High density of different types of exposed active sites is formed, and the small diffusion paths, which enhances the electron transfer in the 2D structures, can successfully aid the charge collection process in the electrocatalytic hydrogen evolution reactions. In this review, the key parameters to improve the catalyst performance of 2D TMDs in electrochemical hydrogen evolution reaction (HER) processes are discussed in detail and the most recent developments in the field are summarized, focusing on the improvement of the electrocatalytic activity of 2D TMDs. This review delivers deep insight for the clear understanding of the potential of 2D TMDs nanoscale materials as electrocatalysts for HER, suggesting the development of new type of catalyst with efficient activity in HER as well as other renewable energy fields.
Coupling Methanol Oxidation with Hydrogen Evolution on Bifunctional Co‐Doped Rh Electrocatalyst for Efficient Hydrogen Generation
Authors: Guo Yan , Yang Xiaobo , Liu Xingchen , Tong Xili , Yang Nianjun
Published: October 2022

Efficient hydrogen production from electrochemical overall water splitting requires high‐performance electrocatalysts for hydrogen evolution reaction (HER) and a fast oxidation reaction to replace sluggish oxygen evolution reaction. Herein, Co‐doped Rh nanoparticles are thus grown on carbon black using Co nanosheets as the bridge. These nanoparticles with a size of ≈1.94 nm exhibit the overpotential of as low as 2 mV at 10 mA cm−2 for the HER, and a mass activity of as high as 889 mA mg−1 for the methanol oxidation reaction (MOR) in alkaline media. As confirmed by density functional theory simulations, such excellent activity originates from Co‐doping, which reduces reaction energy barriers for both the rate‐determining step of a Volmer process during the HER and the conversion of *CO to COOH* during the MOR (namely the enhanced adsorption of H2O and COOH*). Coupling boosted HER on the cathode with accelerated MOR on the anode, efficient H2 generation is achieved. This two‐electrode cell only requires a cell voltage of 1.545 V at 10 mA cm−2 with impressive long‐life cycling stability. Such performance even outperforms that of commercial Pt/C || IrO2 cell. This study offers a new strategy to achieve efficient HER from overall water splitting.
Bone‐Adhesive Anisotropic Tough Hydrogel Mimicking Tendon Enthesis
Authors: Choi Suji , Moon Jong Ryul , Park Nuri , Im Jihye , Kim Ye Eun , Kim Ji‐Heung , Kim Jaeyun
Published: October 2022

Tendon consists of soft collagen, yet it is mechanically strong and firmly adhered to the bone owing to its hierarchically anisotropic structure and unique tendon‐to‐bone integration (enthesis), respectively. Despite the recent advances in biomaterials, hydrogels simultaneously providing tendon‐like high mechanical properties and strong adhesion to bone‐mimicking enthesis is still challenging. Here, a strong, stiff, and adhesive triple‐network (TN) anisotropic hydrogel that mimics a bone‐adhering tendon is shown. The tough adhesive TN hydrogel is developed by combining imidazole‐containing polyaspartamide (providing multiple hydrogen bonds to the bone surface) and energy‐dissipative alginate–polyacrylamide double‐network. To mimic the anisotropic structure and high mechanical properties of tendons, the bone‐adhered TN hydrogel is linearly stretched and subsequently fixed via secondary cross‐linking. The resulting hydrogel exhibits high tensile modulus and strength while maintaining a high bone adhesion without chemical modification of the bone surface. Furthermore, a bone–ligament–bone structure with strong bone adhesion reminiscent of the natural ligament is realized.
Near‐Infrared Nano‐Optogenetic Activation of Cancer Immunotherapy via Engineered Bacteria
Authors: Zhu Xiaoqiang , Chen Sihan , Hu Xiuwen , Zhao Lijun , Wang Yiqian , Huang Jinzhao , Chen Jiawen , Qiu Yuzhi , Zhang Xuefei , Wang Mengdie , Yang Xiangliang , Zhang Yan , Zhu Yanhong
Published: October 2022

Certain anaerobic microbes with the capability to colonize the tumor microenvironment tend to express the heterologous gene in a sustainable manner, which will inevitably compromise the therapeutic efficacy and induce off‐tumor toxicity in vivo. To improve the therapeutic precision and controllability of bacteria‐based therapeutics, Escherichia coli Nissle 1917 (EcN), engineered to sense blue light and release the encoded flagellin B (flaB), is conjugated with lanthanide upconversion nanoparticles (UCNPs) for near‐infrared (NIR) nano‐optogenetic cancer immunotherapy. Upon 808 nm photoirradiation, UCNPs emit at the blue region to photoactivate the EcN for secretion of flaB, which subsequently binds to Toll‐like receptor 5 expressed on the membrane of macrophages for activating immune response via MyD88‐dependent signal pathway. Such synergism leads to significant tumor regression in different tumor models and metastatic tumors with negligible side effects. These studies based on the NIR nano‐optogenetic platform highlight the rational of leveraging the optogenetic tools combined with natural propensity of certain bacteria for cancer immunotherapy.
Boosting Perovskite Solar Cells Efficiency and Stability: Interfacial Passivation of Crosslinked Fullerene Eliminates the “Burn‐in” Decay
Authors: Ding Changzeng , Yin Li , Wang Jinlong , Larini Valentina , Zhang Lianping , Huang Rong , Nyman Mathias , Zhao Liyi , Zhao Chun , Li Weishi , Luo Qun , Shen Yanbin , Österbacka Ronald , Grancini Giulia , Ma Chang‐Qi
Published: October 2022

Perovskite solar cells (PSCs) longevity is nowadays the bottleneck for their full commercial exploitation. Although lot of research is ongoing, the initial decay of the output power – an effect known as “burn‐in” degradation happening in the first 100 h – is still unavoidable, significantly reducing the overall performance (typically of >20%). In this paper, the origin of the “burn‐in” degradation in n‐i‐p type PSCs is demonstrated that is directly related to Li+ ions migration coming from the SnO2 electron transporting layer visualized by time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) measurements. To block the ion movement, a thin cross‐linked [6,6]‐phenyl‐C61‐butyric acid methyl ester layer on top of the SnO2 layer is introduced, resulting in Li+ immobilization. This results in the elimination of the “burn‐in” degradation, showing for the first time a zero “burn‐in” loss in the performances while boosting device power conversion efficiency to >22% for triple‐cation‐based PSCs and >24% for formamidinium‐based (FAPbI3) PSCs, proving the general validity of this approach and creating a new framework for the realization of stable PSCs devices.
Porous Covalent Organic Polymer Coordinated Single Co Site Nanofibers for Efficient Oxygen‐Reduction Cathodes in Polymer Electrolyte Fuel Cells
Authors: Yang Bolong , Han Qing , Han Linkai , Leng Yiming , O'Carroll Thomas , Yang Xiaoxuan , Wu Gang , Xiang Zhonghua
Published: October 2022

Nitrogen‐coordinated single‐cobalt‐atom electrocatalysts, particularly ones derived from high‐temperature pyrolysis of cobalt‐based zeolitic imidazolate frameworks (ZIFs), have emerged as a new frontier in the design of oxygen reduction cathodes in polymer electrolyte fuel cells (PEFCs) due to their enhanced durability and smaller Fenton effects related to the degradation of membranes and ionomers compared with emphasized iron‐based electrocatalysts. However, pyrolysis techniques lead to obscure active‐site configurations, undesirably defined porosity and morphology, and fewer exposed active sites. Herein, a highly stable cross‐linked nanofiber electrode is directly prepared by electrospinning using a liquid processability cobalt‐based covalent organic polymer (Co‐COP) obtained via pyrolysis‐free strategy. The resultant fibers can be facilely organized into a free‐standing large‐area film with a uniform hierarchical porous texture and a full dispersion of atomic Co active sites on the catalyst surface. Focused ion beam‐field emission scanning electron microscopy and computational fluid dynamics experiments confirm that the relative diffusion coefficient is enhanced by 3.5 times, which can provide an efficient route both for reactants to enter the active sites, and drain away the produced water efficiently. Resultingly, the peak power density of the integrated Co‐COP nanofiber electrode is remarkably enhanced by 1.72 times along with significantly higher durability compared with conventional spraying methods. Notably, this nanofabrication technique also maintains excellent scalability and uniformity.
A Single‐Administration Microneedle Skin Patch for Multi‐Burst Release of Vaccine against SARS‐CoV‐2
Authors: Tran Khanh T. M. , Gavitt Tyler D. , Le Thinh T. , Graichen Adam , Lin Feng , Liu Yang , Tulman Edan R. , Szczepanek Steven M. , Nguyen Thanh D.
Published: October 2022

The necessity for multiple injections and cold‐chain storage has contributed to suboptimal vaccine utilization, especially in pandemic situations. Thermally‐stable and single‐administration vaccines hold a great potential to revolutionize the global immunization process. Here, a new approach to thermally stabilize protein‐based antigens is presented and a new high‐throughput antigen‐loading process is devised to create a single‐administration, pulsatile‐release microneedle (MN) patch which can deliver a recombinant SARS‐CoV‐2 S1‐RBD protein—a model for the COVID‐19 vaccine. Nearly 100% of the protein antigen could be stabilized at temperatures up to 100 °C for at least 1 h and at an average human body temperature (37 °C) for up to 4 months. Arrays of the stabilized S1‐RBD formulations can be loaded into the MN shells via a single‐alignment assembly step. The fabricated MNs are administered at a single time into the skin of rats and induce antibody response which could neutralize authentic SARS‐CoV‐2 viruses, providing similar immunogenic effect to that induced by multiple bolus injections of the same antigen stored in conventional cold‐chain conditions. The MN system presented herein could offer the key solution to global immunization campaigns by avoiding low patient compliance, the requirement for cold‐chain storage, and the need for multiple booster injections.
Recent Progress of Wearable Piezoelectric Pressure Sensors Based on Nanofibers, Yarns, and Their Fabrics via Electrospinning
Authors: Zhi Chuanwei , Shi Shuo , Si Yifan , Fei Bin , Huang Haitao , Hu Jinlian
Published: October 2022

Highly sensitive flexible pressure sensors are extensively investigated for various applications, such as electronic skin, human physiological monitoring, and artificial intelligence. However, traditional fabrication technologies are hard to realize the large‐area and mass production of wearable sensing devices. Current trend of miniaturization, systematization, and multifunction has raised the problems of total energy consumption, frequent charging, and reduced usage time. These issues have hindered the progress of wearable sensing electronics. In the light of nanomaterial design, mass production, and facile manufacturing, electrospun piezoelectric pressure sensors offer the best properties of self‐powering, breathability, stretchability, and flexibility, providing ideal interfacing platforms for smart wearables. Tremendous advances have been achieved recently in the high sensitivity, piezoelectric output, composite optimization, and nano‐/microstructure design of nonwoven nanofiber membranes. Nevertheless, how to fulfill real textile‐level integration in consideration of biocompatibility, integration, wearability, geometrical design, multifunction, and systematization remains a big challenge. Therefore, recent progress of piezoelectric pressure sensors from electrospun nanofibers to their fabrics is comprehensively summarized. Plentiful strategies, structure designs, and underlying mechanisms that boost the piezoelectric properties are discussed. Lastly, the challenges and possible solutions for the future electrospinning‐based pressure sensing systems are proposed.
Black Silicon Revisited as an Ultrabroadband Perfect Infrared Absorber over 20 μm Wavelength Range
Authors: Sarkar Sreyash , Elsayed Ahmed A. , Sabry Yasser M. , Marty Frédéric , Drévillon Jérémie , Liu Xiaoyi , Liang Zhongzhu , Richalot Elodie , Basset Philippe , Nefzaoui Elyes , Bourouina Tarik
Published: October 2022

Black silicon properties are investigated in the wavelength range extending from 0.2 to 25 μm with a focus on the mid‐infrared (MIR). It is demonstrated that concurrently increasing the initial level of doping of bare silicon, with given limits, enables reaching even higher absorptance and higher spectral range. Unprecedented light absorptance levels are obtained on black silicon with up to 99.5% in the spectral range from 1 to 8 μm and above 90% until 20 μm, leading to ultrabroadband, ultrablack silicon surfaces. The synergetic effects of morphology and volume doping are elucidated; in particular, how the high aspect‐ratio of conical nanostructures plays a crucial role. The experimental findings are analyzed with numerical simulations involving plasmonic effects of highly doped silicon and supported by tomographic processing of microscopy images. Guidelines and corresponding manufacturing routes are provided by which ultrabroadband, ultrablack silicon surfaces can be obtained within minutes of plasma processing, with no need for further functionalization. With the scalable manufacturing involving solely pure silicon, the resulting ultrabroadband perfect absorbers should be of benefit for large‐scale deployment of radiative cooling devices, blackbody infrared light sources, and infrared radiation sensing.
Macrophage Reprogramming with Anti‐miR223‐Loaded Artificial Protocells Enhances In Vivo Cancer Therapeutic Potential
Authors: López‐Cuevas Paco , Xu Can , Severn Charlotte E. , Oates Tiah C. L. , Cross Stephen J. , Toye Ashley M. , Mann Stephen , Martin Paul
Published: October 2022

Several immune cell‐expressed miRNAs (miRs) are associated with altered prognostic outcome in cancer patients, suggesting that they may be potential targets for development of cancer therapies. Here, translucent zebrafish (Danio rerio) is utilized to demonstrate that genetic knockout or knockdown of one such miR, microRNA‐223 (miR223), globally or specifically in leukocytes, does indeed lead to reduced cancer progression. As a first step toward potential translation to a clinical therapy, a novel strategy is described for reprogramming neutrophils and macrophages utilizing miniature artificial protocells (PCs) to deliver anti‐miRs against the anti‐inflammatory miR223. Using genetic and live imaging approaches, it is shown that phagocytic uptake of anti‐miR223‐loaded PCs by leukocytes in zebrafish (and by human macrophages in vitro) effectively prolongs their pro‐inflammatory state by blocking the suppression of pro‐inflammatory cytokines, which, in turn, drives altered immune cell‐cancer cell interactions and ultimately leads to a reduced cancer burden by driving reduced proliferation and increased cell death of tumor cells. This PC cargo delivery strategy for reprogramming leukocytes toward beneficial phenotypes has implications also for treating other systemic or local immune‐mediated pathologies.
Metabolic Rewiring of Kynurenine Pathway during Hepatic Ischemia–Reperfusion Injury Exacerbates Liver Damage by Impairing NAD Homeostasis
Authors: Xu Bowen , Zhang Peng , Tang Xiaolong , Wang Shiguan , Shen Jing , Zheng Yuanwen , Gao Chao , Mi Ping , Zhang Cuijuan , Qu Hui , Li Shiyang , Yuan Detian
Published: October 2022

Hepatic ischemia–reperfusion (IR) injury remains a common issue lacking effective strategy and validated pharmacological targets. Here, using an unbiased metabolomics screen, this study finds that following murine hepatic IR, liver 3‐hydroxyanthranilic acid (3‐HAA) and quinolinic acid (QA) decline while kynurenine and kynurenic acid (KYNA) increase. Kynurenine aminotransferases 2, functioning at the key branching point of the kynurenine pathway (KP), is markedly upregulated in hepatocytes during ischemia, shifting the kynurenine metabolic route from 3‐HAA and QA to KYNA synthesis. Defects in QA synthesis impair de novo nicotinamide adenine dinucleotide (NAD) biosynthesis, rendering the hepatocytes relying on the salvage pathway for maintenance of NAD and cellular antioxidant defense. Blocking the salvage pathway following IR by the nicotinamide phosphoribosyltransferase inhibitor FK866 exacerbates liver oxidative damage and enhanced IR susceptibility, which can be rescued by the lipid peroxidation inhibitor Liproxstatin‐1. Notably, nicotinamide mononucleotide administration once following IR effectively boosts NAD and attenuated IR‐induced oxidative stress, inflammation, and cell death in the murine model. Collectively, the findings reveal that metabolic rewiring of the KP partitions it away from NAD synthesis in hepatic IR pathophysiology, and provide proof of concept that NAD augmentation is a promising therapeutic measure for IR‐induced liver injury.
Anisotropic Microgels by Supramolecular Assembly and Precipitation Polymerization of Pyrazole‐Modified Monomers
Authors: Grabowski Frédéric , Petrovskii Vladislav S. , Fink Fabian , Demco Dan Eugen , Herres‐Pawlis Sonja , Potemkin Igor I. , Pich Andrij
Published: October 2022

Soft colloidal macromolecular structures with programmable chemical functionalities, size, and shape are important building blocks for the fabrication of catalyst systems and adaptive biomaterials for tissue engineering. However, the development of the easy upscalable and template‐free synthesis methods to obtain such colloids lack in understanding of molecular interactions that occur in the formation mechanisms of polymer colloids. Herein, a computer simulation‐driven experimental synthesis approach based on the supramolecular self‐assembly followed by polymerization of tailored pyrazole‐modified monomers is developed. Simulations for a series of pyrazole‐modified monomers with different numbers of pyrazole groups, different length and polarity of spacers between pyrazole groups and the polymerizable group are first performed. Based on simulations, monomers able to undergo π–π stacking and guide the formation of supramolecular bonds between polymer segments are synthesized and these are used in precipitation polymerization to synthesize anisotropic microgels. This study demonstrates that microgel morphologies can be tuned from spherical, raspberry‐like to dumbbell‐like by the increase of the pyrazole‐modified monomer loading, which is concentrated at periphery of growing microgels. Combining experimental and simulation results, this work provides a quantitative and predictive approach for guiding microgel design that can be further extended to a diversity of colloidal systems and soft materials with superior properties.
A Zinc–Bromine Battery with Deep Eutectic Electrolytes
Authors: Heo Jiyun , Shin Kyungjae , Kim Hee‐Tak
Published: October 2022

A deep eutectic solvent (DES) is an ionic liquid‐analog electrolyte, newly emerging due to its low cost, easy preparation, and tunable properties. Herein, a zinc–bromine battery (ZBB) with a Zn‐halide‐based DES electrolyte prepared by mixing ZnBr2, ZnCl2, and a bromine‐capturing agent is reported. The water‐free DES electrolyte allows a closed‐cell configuration for the ZBB owing to the prevention of Br2 evaporation and H2 evolution. It is found that the Cl− anion changes the structure of the zinc‐halide complex anions and demonstrated that it improves the ion mobility and electrode reaction kinetics. The DES electrolyte with the optimized ZnCl2 composition shows much higher rate capability and a cycle life 90 times longer than that of a ZnCl2‐free DES electrolyte. A pouch‐type flexible ZBB battery based on the DES electrolyte exhibits swelling‐free operation for more than 120 cycles and stable operation under a folding test, suggesting its potential in consumer applications such as wearable electronics.
N6‐Methyladenosine‐Modified CBX1 Regulates Nasopharyngeal Carcinoma Progression Through Heterochromatin Formation and STAT1 Activation
Authors: Zhao Yin , Huang Shengyan , Tan Xirong , Long Liufen , He Qingmei , Liang Xiaoyu , Bai Jiewen , Li Qingjie , Lin Jiayi , Li Yingqin , Liu Na , Ma Jun , Chen Yupei
Published: October 2022

Epitranscriptomic remodeling such as N6‐methyladenosine (m6A) modification plays a critical role in tumor development. However, little is known about the underlying mechanisms connecting m6A modification and nasopharyngeal carcinoma (NPC) progression. Here, CBX1 is identified, a histone methylation regulator, to be significantly upregulated with m6A hypomethylation in metastatic NPC tissues. The m6A‐modified CBX1 mRNA transcript is recognized and destabilized by the m6A reader YTHDF3. Furthermore, it is revealed that CBX1 promotes NPC cell migration, invasion, and proliferation through transcriptional repression of MAP7 via H3K9me3‐mediated heterochromatin formation. In addition to its oncogenic effect, CBX1 can facilitate immune evasion through IFN‐γ‐STAT1 signaling‐mediated PD‐L1 upregulation. Clinically, CBX1 serves as an independent predictor for unfavorable prognosis in NPC patients. The results reveal a crosstalk between epitranscriptomic and epigenetic regulation in NPC progression, and shed light on the functions of CBX1 in tumorigenesis and immunomodulation, which may provide an appealing therapeutic target in NPC.
Force‐Induced Synergetic Pigmentary and Structural Color Change of Liquid Crystalline Elastomer with Nanoparticle‐Enhanced Mechanosensitivity
Authors: Sun Chang , Zhang Shuoning , Ren YunXiao , Zhang Jianying , Shen Jiyuan , Qin Shengyu , Hu Wei , Zhu Siquan , Yang Huai , Yang Dengke
Published: October 2022

The ability of some animals to rapidly change their colors can greatly improve their chances of escaping predators or hunting prey. A classic example is cephalopods, which can rapidly shift through a wide range of colors. This ability is based on the synergetic effect of the change of pigmentary and structural colors exhibited by their own two categories of color‐changing cells: supernatant chromatophores offer various pigmentary colors and lower iridophores or leucophores reflect the different structural colors by adjusting their periodicities. Here, a mechanochromic liquid crystalline elastomer with force‐induced synergetic pigmentary and structural color change, whose mechanosensitivity is enhanced by the stress‐concentration induced by the doped nanoparticle, is presented. The materials have a large color‐changing gamut and high mechanochromic sensitivity, which exhibit great potential in the field of mechanical detectors, sensors, and anti‐counterfeiting materials.
Memristor‐Based Intelligent Human‐Like Neural Computing
Authors: Wang Shengbo , Song Lekai , Chen Wenbin , Wang Guanyu , Hao En , Li Cong , Hu Yuhan , Pan Yu , Nathan Arokia , Hu Guohua , Gao Shuo
Published: October 2022

Humanoid robots, intelligent machines resembling the human body in shape and functions, cannot only replace humans to complete services and dangerous tasks but also deepen the own understanding of the human body in the mimicking process. Nowadays, attaching a large number of sensors to obtain more sensory information and efficient computation is the development trend for humanoid robots. Nevertheless, due to the constraints of von Neumann‐based structures, humanoid robots are facing multiple challenges, including tremendous energy consumption, latency bottlenecks, and the lack of bionic properties. Memristors, featured with high similarity to the biological elements, play an important role in mimicking the biological nervous system. The memristor‐based nervous system allows humanoid robots to obtain high energy efficiency and bionic sensing properties, which are similar properties to the biological nervous system. Herein, this article first reviews the biological nervous system and memristor‐based nervous system thoroughly, including the structures and also the functions. The applications of memristor‐based nervous systems are introduced, the difficulties that need to be overcome are put forward, and future development prospects are also discussed. This review can hopefully provide an evolutionary perspective on humanoid robots and memristor‐based nervous systems.
Boosting Photoelectrochemical Ethanol Evolution on Reduced Graphene Oxide Functionalized Photocathode
Authors: Jung Mi , Kim Chang Woo , Kim So Yeon , Pawar Amol U. , Lee Don Keun , Kang Young Soo
Published: October 2022

Herein, a reduced graphene oxide (rGO) functionalized photocathode is studied for selective production of solar liquid fuels depending on dark and solar light illumination condition. rGO functionalized photocathode with p–n junction at the core–shell interface of ZnO@ZnTe is prepared with a three‐step synthetic process. Preparation of ZnO nanorod, formation of ZnTe on ZnO nanorod by anion‐exchange and then, finally, rGO layers are functionalized on the surface of ZnO@ZnTe photocathode. The photoelectrochemical (PEC) system of BiVO4∥KHCO3∥ZnO@ZnTe@rGO combination is introduced for selective solar liquid fuel production by CO2 reduction reaction (CO2RR). Functionalization of rGO layers on photocathode enables the multi‐electron shuttling function for the enhanced charge transfer efficiency due to its large charge capacitance, which results in producing liquid fuels such as HCHO and EtOH selectively as solar liquid fuels. These results in this work clearly demonstrate a possibility of solar liquid fuel product selectivity by PEC CO2RR.
Hard and Soft Acid and Base (HSAB) Engineering for Efficient and Stable Sn‐Pb Perovskite Solar Cells
Authors: Yeom Kyu‐Woong , Lee Do‐Kyoung , Park Nam‐Gyu
Published: October 2022

Regulation of Lewis acid‐base adduct intermediate is more critical for the dual metal ions of Sn2+ and Pb2+ than for the single metal ion such as Pb2+ in preparing high quality perovskite films. It has been reported here that the photovoltaic performance of Sn‐Pb alloyed perovskite solar cells is dependent on the interaction between metal ions and Lewis base additives. Urea and thiourea are selected as an O‐ and a S‐donor, respectively, which is used as an additive in the precursor solution including equimolar SnI2 and PbI2 together with organic iodides of formamidinium iodide and methylammonium iodide, forming a nominal composition of FA0.5MA0.5Pb0.5Sn0.5I3. Open‐circuit voltage (Voc) is increased while maintaining short‐circuit photocurrent density (Jsc) after the addition of urea. On the other hand, both Jsc and Voc are simultaneously increased by adding thiourea, leading to a considerable increase in power conversion efficiency from 14.58% (control) to 18.59%. A strong interaction between the relatively soft Sn2+, compared to Sn4+, and the soft sulfur in thiourea, associated with hard and soft acid and base theory, suppresses effectively a disproportionation reaction of 2Sn2+→ Sn4+ + Sn0, which results in a substantial enhancement of carrier lifetime and consequently photovoltaic performance.
Promoting Surface Reconstruction of NiFe Layered Double Hydroxide for Enhanced Oxygen Evolution
Authors: Lei Hang , Ma Liang , Wan Qixiang , Tan Shaozao , Yang Bo , Wang Zilong , Mai Wenjie , Fan Hong Jin
Published: October 2022

A dynamic surface reconstruction of oxide electrocatalysts in alkaline media is widely observed especially for layered double hydroxide (LDH), but little is known about how to promote the reconstruction toward desired surfaces for improved oxygen evolution reaction (OER). Here, surface reconstruction of NiFe LDH nanosheets is successfully induced to a higher degree via in situ sulfur doping than that by natural electrochemical activation. Theoretical calculations, operando Raman, and various ex situ characterizations reveal the S anion‐induced effect can lower the energy barrier and facilitate the phase transformation into highly active S‐doped oxyhydroxides. The generated S‐NixFeyOOH can optimize the intermediate adsorption and facilitate the OER kinetics. The reconstructed S‐oxyhydroxides catalyst presents superior OER activity and long‐term durability compared to undoped ones. This work provides a structure–composition–activity relationship during the in situ surface restructuring of NiFe LDH pre‐catalysts.
Synergistic Design of Multifunctional Interfacial Zn Host toward Practical Zn Metal Batteries
Authors: Park Jung Been , Choi Changhoon , Park Jong Hyun , Yu Seungho , Kim Dong‐Wan
Published: October 2022

Aqueous Zn metal batteries (ZMBs) are receiving attention as large‐scale energy storage systems owing to their high theoretical capacity, low toxicity, and the abundance of Zn. However, Zn anodes still undergo undesired dendrite growth and intrinsic side reactions, thereby hindering the practical application of ZMBs. In this study, a multifunctional porous zincophilic carbon host (FPCH) assisted by a thin ZnO interphase (ZI) on bare Zn (FPCH‐ZI/Zn) is rationally designed as the interfacial host for stable Zn deposition/dissolution processes to reduce the limitations of Zn anodes. Hydrophobic FPCH with large specific surface areas and zincophilic oxygen‐based functional groups induce a uniform distribution of electric field/Zn2+ flux and low nucleation overpotential and restrain side reactions. Additionally, hydrophilic ZI ensures sufficient quantities of the electrolyte are absorbed into FPCH‐ZI/Zn; it complements the shortcomings (low hygroscopicity of the electrolyte) of hydrophobic FPCH, depositing Zn inside the host. Consequently, the symmetric FPCH‐ZI/Zn cells exhibit excellent cycling performances with low‐voltage polarization, even under harsh operating conditions. Furthermore, in the MnO2∥Zn full‐cell tests, the FPCH‐ZI/Zn full cells exhibit superb long‐term cyclability compared to that of bare Zn under real‐world operating conditions (N/P ratio: ≈7.3), indicating the availability of FPCH‐ZI/Zn for practical ZMBs.
A Biomimetic Soft‐Rigid Hybrid Finger with Autonomous Lateral Stiffness Enhancement
Authors: Zhou Peiwei , Zhang Ningbin , Gu Guoying
Published: October 2022

The application of soft robotics improves the compliance of robotic fingers, which, however, usually loses sufficient stiffness. Here, a biomimetic soft‐rigid hybrid (BSH) finger that can achieve both inherent compliance and autonomous lateral stiffness enhancement is proposed. Driven by pneumatic artificial muscles, the proposed two‐joined BSH finger can produce two flexion degrees of freedom (DOFs) and one lateral DOF motion. Imitating the human finger anatomy, the BSH finger is designed with elliptical bony ridges and eccentrically arranged ligaments. By leveraging the contact interference of the ridges and tensioning of the ligaments, the lateral stiffness of the BSH finger can be autonomously enhanced through finger flexion. During its natural stage, the lateral stiffness is relatively low to ensure mobility and compliance, while in its flexion stage, its lateral stiffness can increase to resist lateral deflection and high payload. To further investigate the advantages of the design, four BSH fingers are assembled into a robotic hand prototype with three grasping types including enveloping grasp, precise pinch, and power grasp. Experimental results demonstrate that the robotic hand prototype is capable of grasping various objects with a wide range of diameters, lengths, thicknesses, and weights, which will verify the effectiveness of the design methodology.
The relationship between chlorophyllous spores and mycorrhizal associations in ferns: evidence from an evolutionary approach
Authors: Mellado‐Mansilla Daniela , Testo Weston , Sundue Michael A. , Zotz Gerhard , Kreft Holger , Coiro Mario , Kessler Michael
Published: October 2022

Premise

Approximately 14% of all fern species have physiologically active chlorophyllous spores that are much more short‐lived than the more common and dormant achlorophyllous spores. Most chlorophyllous‐spored species (70%) are epiphytes and account for almost 37% of all epiphytic ferns. Chlorophyllous‐spored ferns are also overrepresented among fern species in habitats with waterlogged soils, of which nearly 60% have chlorophyllous spores. Ferns in these disparate habitat types also have a low incidence of mycorrhizal associations. We therefore hypothesized that autotrophic chlorophyllous spores represent an adaptation of ferns to habitats with scarce mycorrhizal associations.

Methods

We evaluated the coevolution of chlorophyllous spores and mycorrhizal associations in ferns and their relation to habitat type using phylogenetic comparative methods.

Results

Although we did not find support for the coevolution of spore type and mycorrhizal associations, we did find that chlorophyllous spores and the absence of mycorrhizal associations have coevolved with epiphytic and waterlogged habitats. Transition rates to epiphytic and waterlogged habitats were significantly higher in species with chlorophyllous spores compared to achlorophyllous lineages.

Conclusions

Spore type and mycorrhizal associations appear to play important roles in the radiation of ferns into different habitat types. Future work should focus on clarifying the functional significance of these associations.
Size reduction and skull shape parallelism following the evolutionary forest‐to‐savanna transition in Platyrrhini monkeys
Authors: Cáceres Nilton , Cerezer Felipe O. , Bubadué Jamile
Published: October 2022

There are strong physiological and behavioral differences that allow animals to live in forests versus savannas. For example, terrestrial forest‐dwelling mammals tend to be small compared to species living in savannas. Robust capuchin monkeys (genus Sapajus) are widespread in tropical South America, occurring in both forest and savanna environments, with forest species considered basal in an evolutionary context. Whether or not skull shape and size variations are associated with variation in resource use remains unknown, particularly for the two species living in savanna (Sapajus libidinosus and S. cay). Here we show that savanna species present convergent size and skull characteristics that may facilitate living in this new environment. Geometric morphometric methods were used to assess skull size and shape variation for 184 Sapajus specimens distributed across South America. We used phylogenetic generalized least squares to test size against environmental variables and multivariate morphological trajectories/partial least square analyses on the skull shape to detect shape differences in specimens between forest and savanna biomes. Our findings reveal Sapajus size reduction in the evolutionary transition from forest to savanna, a process related to increasing seasonality. Moreover, we found morphological parallelism in the skull (e.g., muzzle shortening) and (large) molars in the two savanna species, features that may facilitate the processing of harder food such as fallback resources. We associate these phenotypic differences to the evolutionary process of colonizing the savannas by primates (including early hominins), leading to morphological adaptations to tolerate stressful, seasonal environments, such as body size reduction and ingestion and mastication of tough foods.
Dental tissue proportions and linear dimensions of Sima de los Huesos lower incisors
Authors: Lockey Annabelle Louise , Martín‐Francés Laura , Arsuaga Juan Luis , Bermúdez de Castro José María , Martinón‐Torres María
Published: October 2022

Objectives

To assess the phenotypic affinities of the Sima de los Huesos (SH) mandibular incisors dental tissue proportions, and radicular dimensions, relative to Neandertals, recent modern humans (RMH), and a large comparative sample of Pleistocene hominins.

Materials and Methods

Two dimensional (2D) and three dimensional (3D) data were extracted from SH (n = 22) incisors, and compared with specimens from Krapina (n = 6) and Ehringsdorf (n = 2), RMH (n = 42), as well as a comparative sample of hominins from the literature (n = 244). We calculated average enamel thickness (AET), relative enamel thickness (RET) and radicular variables (cervical area [CA] and root surface area [RSA], root linear dimensions [RL], dentine and pulp volume [RDV, RPV, TRV]).

Results

We found that SH incisor crown variables were generally undiagnostic for 2D and 3D AET and 2D RET. Trends indicated thicker 3D RET in RMH relative to SH hominins, Tighenif hominins, and Neandertals. The SH and Neandertal mandibular incisors share similar RL, RSA, and root tissue volumes when compared to other extinct members of Homo. Relative to all other extinct hominins examined here, SH incisors display a relatively narrow cervical labio‐lingual diameter. Finally, we found a weak correlations in SH and RMH between the crown and root variables.

Discussion

This study confirms that SH mandibular incisors' dental tissue proportions and root dimensions align more closely to Neandertals. However, the complete set of Neandertal apomorphies is not present within SH mandibular incisors. SH incisors concur with traits reported in SH canines, and contrasting patterns in the molars, revealing a dichotomy between the anterior and posterior teeth for dental tissue proportions.
Improving community health‐care systems’ early detection of cognitive decline and dementia
Authors:   PAD 20/20 Work Group on Community‐Based Detection of Cognitive Decline and Dementia
Published: October 2022

Preliminary estimates suggest that current global health‐care systems lack the resource capacity to provide persons with dementia timely access to diagnosis, treatment, and care. There is an increasing need to improve timely identification of individuals who will likely progress to Alzheimer's disease (AD) dementia particularly among under‐represented, underserved, and vulnerable populations. The rapidly evolving area of bioinformatics of health system data and the emergence of fluid‐based biomarkers for pre‐symptomatic AD may provide an innovative strategic option for health system planners. A think‐tank style meeting entitled “The Campaign to Prevent Alzheimer's Disease Work Group on Community‐Based Detection and Assessment of Cognitive Decline” developed recommendations to guide future sustainability activities, public policy campaigns, and implementation pilots. The group identified and explored different pathways of community‐based detection using electronic health records, from different international health‐care systems, to detect and surveil individuals with early possible cognitive impairment.
Photo‐controllable Luminescence from Radicals Leading to Ratiometric Emission Switching via Dynamic Intermolecular Coupling
Authors: Jin Jia‐Ming , Chen Wen‐Cheng , Tan Ji‐Hua , Li Yang , Mu Yingxiao , Zhu Ze‐Lin , Cao Chen , Ji Shaomin , Hu Dehua , Huo Yanping , Zhang Hao‐Li , Lee Chun‐Sing
Published: October 2022

The development of photoinduced luminescent radicals with dynamic emission color is still challenging. Herein we report a novel molecular radical system (TBIQ) that shows photo‐controllable luminescence, leading to a wide range of ratiometric color changes via light excitation. The conjugated skeleton of TBIQ is decorated with steric‐demanding tertiary butyl groups that enable appropriate intermolecular interaction to make dynamic intermolecular coupling possible for controllable behaviors. We reveal that the helicenic pseudo‐planar conformation of TBIQ experiences a planarization process after light excitation, leading to more compactly stacked supermolecules and thus generating radicals via intermolecular charge transfer. The photo‐controllable luminescent radical system is employed for a high‐level information encryption application. This study may offer unique insight into molecular dynamic motion for optical manufacturing and broaden the scope of smart‐responsive materials for advanced applications.
Precisely Tailoring Heterometallic Polyoxotitanium Clusters for the Efficient and Selective Photocatalytic Oxidation of Hydrocarbons
Authors: Gao Mei‐Yan , Bai Hui , Cui Xiaofeng , Liu Shuyan , Ling Shan , Kong Tingting , Bai Bing , Hu Canyu , Dai Yitao , Zhao Yingguo , Zhang Lei , Zhang Jian , Xiong Yujie
Published: October 2022

Photocatalysis is a promising yet challenging approach for the selective oxidation of hydrocarbons to valuable oxygenated chemicals with O2 under mild conditions. In this work, we report an atomically precise material model to address this challenge. The key to our solution is the rational incorporation of Fe species into polyoxotitanium cluster to form a heterometallic Ti4Fe1 cocrystal. This newly designed cocrystal cluster, which well governs the energy and charge transfer as evidenced by spectroscopic characterizations and theoretical calculations, enables the synergistic process involving C(sp3)−H bond activation by photogenerated holes and further reactions by singlet oxygen (1O2). Remarkably, the cocrystal Ti4Fe1 cluster achieves efficient and selective oxidation of hydrocarbons (C5 to C16) into aldehydes and ketones with a conversion rate up to 12 860 μmol g−1 h−1, 5 times higher than that of Fe‐doped Ti3Fe1 cluster. This work provides insights into photocatalyst design at atomic level enabling synergistic catalysis.
Dissolution Dynamic Nuclear Polarization of the 77Se Nucleus
Authors: Suh Eul Hyun , Ratnakar James , Singh Jaspal , Kovacs Zoltan
Published: October 2022

77Se is a spin
, low sensitivity nucleus with a natural abundance of 7.6 %. Although 77Se NMR is very useful in the characterization of selenium containing molecules including seleno‐proteins, the detection of 77Se is challenging in biological samples without enrichment. Therefore, the goal of this work was to establish whether the 77Se signal could be enhanced in the liquid state by dissolution dynamic nuclear polarization (DNP) NMR without the need of enrichment. The dominant spin‐lattice relaxation mechanism for 77Se is via chemical shift anisotropy, which is highly dependent on the molecular symmetry. Here we tested three selenium compounds (sodium selenate, sodium selenite and selenocystine) with different molecular symmetries in dissolution DNP experiments and demonstrated that 77Se DNP using commercially available hardware is feasible but the achieved NMR signal enhancements (1368‐fold for selenate, 125‐fold for selenite and no enhancement for selenocystine at 9.4 T) were strongly dependent on molecular symmetry.
Thermal properties of geopolymer composites containing microencapsulated phase change materials
Authors: Pławecka Kinga , Bąk Agnieszka , Bazan Patrycja , Łach Michał
Published: October 2022

The main objective of this paper is to investigate the possibility of using phase change materials (PCMs) as one of the components of a geopolymer and to determine the effect of PCMs addition on the thermal properties of the geopolymer composite obtained. This paper presents the results of geopolymers produced based on fly ash with the addition of microencapsulated PCMs. The geopolymer composites were prepared by adding 0%, 5%, 10%, and 15% PCM, and the curing process was carried out in two temperature ranges: 60°C and 75°C. A PCM with a melting point of 28°C (MicroCapsPCM28‐slurry [Slovenia]) was used. The composites were subjected to thermal conductivity tests in three temperature ranges (0–20°C; 20–40°C; and 30–50°C). This was followed by specific heat and density tests. In addition, the morphology of the geopolymers was determined by scanning electron microscopy. The results showed that the addition of PCMs to the geopolymer materials significantly reduces their thermal conductivity index (compared to the reference sample). Furthermore, the addition of microencapsulated phase‐change materials caused changes in the specific heat of the materials analyzed.
Influence of particle size of flame‐synthesized carbon nanoparticles on band gap and photoluminescence properties
Authors: Kaur Manpreet , Bharj Jyoti
Published: October 2022

Band gap and photoluminescence (PL) properties were investigated for flame‐synthesized carbon nanoparticles (CNPs) of four different particle size distributions. The particles were collected by varying the flow rates of fuel and oxidizer in a controllable co‐flow diffusion flame. The results indicated the possibility of both direct and indirect band gaps in the synthesized CNPs. The band gaps were found to increase with a decrease in the particle size, thereby exhibiting the quantum confinement effect. The PL properties observed with the pure powdered sample showed strong emission in the green region. However, for samples dispersed in isopropyl alcohol, the emission wavelength shifts towards the blue region, showing strong solvent dependence. The particle size of CNPs, however, only affects the emission peak intensities.