bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical Defects and Energetic Disorder Impact the Energy‐Level Alignment of Functionalized Hexaazatriphenylene Thin Films
Authors: Zhang Li , Berteau-Rainville Melissa , Zhai Tianshu , Wang Yuhao , Wang Qi , Salzmann Ingo , Duhm Steffen
Published: March 2023

The energy‐level alignment (ELA) at interfaces ubiquitous in organic optoelectronic applications is decisive for the device performance. Due to the notoriously low density of free charge carriers in organic thin films, the ELA at organic––inorganic interfaces is determined by gap states and/or tailing states of the frontier molecular orbitals, that is, the highest occupied molecular orbital and the lowest unoccupied molecular orbital (LUMO). Informed by modeling defect energies on the density‐functional theory level, it is deduced from ultraviolet and X‐ray photoelectron spectroscopy data that chemical‐defect induced gap states lead to the substrate‐independent pinning of the Fermi level (EF) to the LUMO for 1,4,5,8,9,12‐hexaazatriphenylene‐2,3,6,7,10,11‐hexacarbonitrile thin films. For 5,6,11,12,17,18‐hexaazatrinaphthylene thin films, the ELA is instead governed by tailing states due to energetic disorder, which put the EF closer to midgap position. It is highlighted in the study that the susceptibility of conjugated organic material to forming chemical and structural defects is key for the ELA at interfaces and, therefore, must be considered in the synthesis of novel materials and their processing into functional structures.
NO2 Gas Sensor Based on Pristine Black Silicon Formed by Reactive Ion Etching
Authors: Ayvazyan Gagik , Ayvazyan Karen , Hakhoyan Levon , Semchenko Alina
Published: March 2023

Nitrogen dioxide (NO2) is a serious environmental pollutant and can cause negative consequences on both human health and vegetation growth. Herein, the possibility and promise of using a resistive sensor based on pristine black silicon (BSi) to detect NO2 at room temperature are investigated. BSi is prepared using plasma‐based reactive ion etching. Scanning electron microscope (SEM) studies show that BSi consists of vertically standing nanoneedles and has a large surface area, which facilitates gas adsorption. The gas‐sensing properties of the BSi‐based sensor are tested for low NO2 concentrations (1–5 ppm). It is found that the prepared sensor samples without posttreatments of BSi exhibit high sensitivity, fast transient response, and good repeatability. In particular, the response and recovery time of the sensor are ≈35 and ≈25 s for 4 ppm NO2 gas exposure, respectively. Besides, the results indicate that the BSi‐based sensor has excellent selectivity. Finally, the sensing mechanism is discussed, the dominating factors of which are the large active sensing area and the vertical arrangement of the BSi nanoneedles. It is believed that with further optimization, BSi has good potential as a functional material for gas sensors.
On updating the results of the control chart using a modified EWMA statistic
Authors: Khan Nasrullah , Aslam Muhammad
Published: March 2023

Khan et al. presented the results using the approximation for the control chart using a modified exponentially weighted moving average (EWMA) statistic. In this paper, we will correct the results using Monte Carlosimulation. We will show that modified EWMA is more efficient than traditional EWMA in terms of average run length.
Distributed event‐triggered control for bipartite consensus under complex cyber‐attacks
Authors: Wu Tong , Cai Guangbin , Wang Jie , Mu Chaoxu
Published: March 2023

Since complex cyber‐attacks and inter‐agent competition pose security risks to multi‐agent systems (MASs), the problem of bipartite consensus control under complex cyber‐attacks studied in this article is more challenging and practical than normal consensus. Firstly, a sliding surface for designing control inputs is presented to overcome the effects of external disturbances and false data injection attacks. The event‐triggered mechanism is constructed to reduce control consumption, and the avoidance of Zeno behavior is demonstrated by analyzing the trigger interval lower bound. Then, considering the existence of aperiodic denial‐of‐service (DoS) attacks, the attack model is analyzed in detail, and the stability of the MAS under complex cyber‐attacks is proved by adopting an inductive way and selecting an appropriate Lyapunov function. Finally, the effectiveness of the presented event‐based control protocol can be seen by simulation.
Implementation of sustainable development goal 8 in European Union countries–A measurement concept and a multivariate comparative analysis
Authors: Grzebyk Mariola , Stec Małgorzata , Hejdukova Pavlina
Published: March 2023

The study attempts to determine a synthetic measure of the level of implementation of Sustainable Development Goal 8 related to promote sustained, inclusive and sustainable economic growth, full and productive employment and decent work for all and conducts a multivariate comparative analysis of EU countries in terms of its implementation. The statistical database contained all 9 variables characterising this goal, collected for 27 EU countries in the period from 2015 to 2020. The research method used was the method of unitarisation zeroed in the dynamic version. The results of the conducted research confirm that there have been positive changes in the implementation of SDG 8 sustainable development in most EU countries in the examined years. This is indicated by the increasing values of the calculated synthetic measure for individual EU27 countries in the examined years. However, in the last examined year, i.e. 2020, the impact of the crisis caused by the COVID 19 pandemic on the achievement of the examined Sustainable Development Goal was observed. In 2020, compared to 2015, 12 EU countries advanced their positions in the EU27 ranking, 3 countries did not change their positions, while 12 countries dropped down in the ranking. The study also assesses two selected EU countries, namely the Czech Republic and Poland (The Czech Republic and Poland are the countries of origin of the authors of this article, with a similar history, located in Central and Eastern Europe and with similar problems of socio‐economic development. These countries also joined the European Union in the same year, 2004) in terms of achieving Sustainable Development Goal 8.
Boosting multivariate structured additive distributional regression models
Authors: Strömer Annika , Klein Nadja , Staerk Christian , Klinkhammer Hannah , Mayr Andreas
Published: March 2023

We develop a model‐based boosting approach for multivariate distributional regression within the framework of generalized additive models for location, scale, and shape. Our approach enables the simultaneous modeling of all distribution parameters of an arbitrary parametric distribution of a multivariate response conditional on explanatory variables, while being applicable to potentially high‐dimensional data. Moreover, the boosting algorithm incorporates data‐driven variable selection, taking various different types of effects into account. As a special merit of our approach, it allows for modeling the association between multiple continuous or discrete outcomes through the relevant covariates. After a detailed simulation study investigating estimation and prediction performance, we demonstrate the full flexibility of our approach in three diverse biomedical applications. The first is based on high‐dimensional genomic cohort data from the UK Biobank, considering a bivariate binary response (chronic ischemic heart disease and high cholesterol). Here, we are able to identify genetic variants that are informative for the association between cholesterol and heart disease. The second application considers the demand for health care in Australia with the number of consultations and the number of prescribed medications as a bivariate count response. The third application analyses two dimensions of childhood undernutrition in Nigeria as a bivariate response and we find that the correlation between the two undernutrition scores is considerably different depending on the child's age and the region the child lives in.
Carbon Dots: Classically Defined versus Organic Hybrids on Shared Properties, Divergences, and Myths
Authors: Liang Weixiong , Sonkar Sumit Kumar , Saini Deepika , Sheriff Kirkland , Singh Buta , Yang Liju , Wang Ping , Sun Ya‐Ping
Published: March 2023

Carbon dots are defined as small carbon nanoparticles with effective surface passivation via organic functionalization. The definition is literally a description of what carbon dots are originally found for the functionalized carbon nanoparticles displaying bright and colorful fluorescence emissions, mirroring those from similarly functionalized defects in carbon nanotubes. In literature more popular than classical carbon dots are the diverse variety of dot samples from “one‐pot” carbonization of organic precursors. On the two different kinds of samples from the different synthetic approaches, namely, the classical carbon dots versus those from the carbonization method, highlighted in this article are their shared properties and apparent divergences, including also explorations of the relevant sample structural and mechanistic origins for the shared properties and divergences. Echoing the growing evidence and concerns in the carbon dots research community on the major presence of organic molecular dyes/chromophores in carbonization produced dot samples, demonstrated and discussed in this article are some representative cases of dominating spectroscopic interferences due to the organic dye contamination that have led to unfound claims and erroneous conclusions. Mitigation strategies to address the contamination issues, including especially the use of more vigorous processing conditions in the carbonization synthesis, are proposed and justified.
Enzyme‐Activatable Polypeptide for Plasma Membrane Disruption and Antitumor Immunity Elicitation
Authors: Liu Jiahui , Li Rong Sheng , Zhang Lei , Wang Jie , Dong Qi , Xu Zhigang , Kang Yuejun , Xue Peng
Published: March 2023

Enzyme‐instructed self‐assembly of bioactive molecules into nanobundles inside cells is conceived to potentially disrupt plasma membrane and subcellular structure. Herein, an alkaline phosphatase (ALP)‐activatable hybrid of ICG‐CF4KYp is facilely synthesized by conjugating photosensitizer indocyanine green (ICG) with CF4KYp peptide via classical Michael addition reaction. ALP‐induced dephosphorylation of ICG‐CF4KYp enables its transformation from small‐molecule precursor into rigid nanofibrils, and such fibrillation in situ causes severe mechanical disruption of cytomembrane. Besides, ICG‐mediated photosensitization causes additional oxidative damage of plasma membrane by lipid peroxidation. Hollow MnO2 nanospheres devote to deliver ICG‐CF4KYp into tumorous tissue through tumor‐specific acidity/glutathione‐triggered degradation of MnO2, which is monitored by fluorescent probing and magnetic resonance imaging. The burst release of damage‐associated molecular patterns and other tumor antigens during therapy effectively triggers immunogenetic cell death and improves immune stimulatory, as demonstrated by the promotion of dendritic cell maturation and CD8+ lymphocyte infiltration, as well as constraint of regulatory T cell population. Taken together, such cytomembrane injury strategy based on peptide fibrillation in situ holds high clinical promise for lesion‐specific elimination of primary, abscopal, and metastatic tumors, which may enlighten more bioinspired nanoplatforms for anticancer theranostics.
Promising Mass‐Productive 4‐Inch Commercial SERS Sensor with Particle in Micro‐Nano Porous Ag/Si/Ag Structure Using in Auxiliary Diagnosis of Early Lung Cancer
Authors: Gao Yuanmei , Zhu Hongyu , Wang Xiaoxiong , Shen Rong , Zhou Xiaoming , Zhao Xiaofei , Li Zhen , Zhang Chao , Lei Fengcai , Yu Jing
Published: March 2023

The construction of commercial surface enhanced Raman scattering (SERS) sensors suitable for clinical applications is a pending problem, which is heavily limited by the low production of high‐performance SERS bases, because they usually require fine or complicated micro/nano structures. To solve this issue, herein, a promising mass‐productive 4‐inch ultrasensitive SERS substrate available for early lung cancer diagnosis is proposed, which is designed with a special architecture of particle in micro‐nano porous structure. Benefitting from the effective cascaded electric field coupling inside the particle‐in‐cavity structure and efficient Knudsen diffusion of molecules within the nanohole, the substrate exhibits remarkable SERS performance for gaseous malignancy biomarker, with the limit of detection is 0.1 ppb and the average relative standard deviation value at different scales (from cm2 to µm2) is ≈16.5%. In practical application, this large‐sized sensor can be further divided into small ones (1 × 1 cm2), and more than 65 chips will be obtained from just one 4‐inch wafer, greatly increasing the output of commercial SERS sensor. Further, a medical breath bag composed of this small chip is designed and studied in detail here, which suggested high‐specificity recognition for lung cancer biomarker in mixed mimetic exhalation tests.
Improving Out‐of‐Plane Charge Mobility and Phase Stability of Dion‐Jacobson Lead‐Free Perovskites via Intercalating π‐Conjugated Aromatic Spacers
Authors: Sun Qian , Shang Ming‐Hui , Fang Zhi , Zheng Yapeng , Hou Xinmei , Yang Weiyou
Published: March 2023

The layered quasi‐2D perovskites are recognized as one of the effective strategies to resolve the big problem of intrinsic phase instability of the perovskites. However, in such configurations, their performance is fundamentally limited due to the correspondingly weakened out‐of‐plane charge mobility. Herein, the π‐conjugated p‐phenylenediamine (PPDA) is introduced as organic ligand ions for rationally designing lead‐free and tin‐based 2D perovskites with the aid of theoretical computation. It is evidenced that both out‐of‐plane charge transport capacity and stability can be significantly enhanced within as‐established quasi‐2D Dion‐Jacobson (DJ) (PPDA)Csn‐1SnnI3n+1 perovskites. The obviously increased electrical conductivity and reduced carrier effective masses are attributed to the enhanced interlayer interactions, limited structural distortions of diamine cations, as well as improved orbital coupling between Sn2+ and I− ions of (PPDA)Csn‐1SnnI3n+1 perovskites. Accordingly, by dimension engineering of the inorganic layer (n), the bandgap (Eg) of quasi‐2D perovskites can be linearly tailored toward the suitable Eg (1.387 eV) with optimal photoelectric conversion efficiency (PCE) of 18.52%, representing their great potential toward promising applications in advanced solar cells.
Tailor‐Made Autophagy Cascade Amplification Polymeric Nanoparticles for Enhanced Tumor Immunotherapy
Authors: Long Xuehua , Wang Huiqi , Yan Jianqin , Li Yifei , Dong Xue , Tian Sijia , Sun Yong , Luo Kui , He Bin , Liang Yan
Published: March 2023

Chemotherapeutics can induce immunogenic cell death (ICD) by triggering autophagy and mediate antitumor immunotherapy. However, using chemotherapeutics alone can only cause mild cell‐protective autophagy and be incapable of inducing sufficient ICD efficacy. The participation of autophagy inducer is competent to enhance autophagy, so the level of ICD is promoted and the effect of antitumor immunotherapy is highly increased. Herein, tailor‐made autophagy cascade amplification polymeric nanoparticles STF@AHPPE are constructed to enhance tumor immunotherapy. Arginine (Arg), polyethyleneglycol–polycaprolactone, and epirubicin (EPI) are grafted onto hyaluronic acid (HA) via disulfide bond to form the AHPPE nanoparticles and autophagy inducer STF‐62247 (STF) is loaded. When STF@AHPPE nanoparticles target to tumor tissues and efficiently enter into tumor cells with the help of HA and Arg, the high glutathione concentration leads to the cleavage of disulfide bond and the release of EPI and STF. Finally, STF@AHPPE induces violent cytotoxic autophagy and strong ICD efficacy. As compared to AHPPE nanoparticles, STF@AHPPE nanoparticles kill the most tumor cells and show the more obvious ICD efficacy and immune activation ability. This work provides a novel strategy for combining tumor chemo‐immunotherapy with autophagy induction.
Scalable Manufacturing of Environmentally Stable All‐Solid‐State Plant Protein‐Based Supercapacitors with Optimal Balance of Capacitive Performance and Mechanically Robust
Authors: Jiang Shuaicheng , Wei Yanqiang , Li Xiaona , Shi Sheldon Q. , Tian Dan , Fang Zhen , Li Jianzhang
Published: March 2023

The development of advanced biomaterial with mechanically robust and high energy density is critical for flexible electronics, such as batteries and supercapacitors. Plant proteins are ideal candidates for making flexible electronics due to their renewable and eco‐friendly natures. However, due to the weak intermolecular interactions and abundant hydrophilic groups of protein chains, the mechanical properties of protein‐based materials, especially in bulk materials, are largely constrained, which hinders their performance in practical applications. Here, a green and scalable method is shown for the fabrication of advanced film biomaterials with high mechanical strength (36.3 MPa), toughness (21.25 MJ m−3), and extraordinary fatigue‐resistance (213 000 times) by incorporating tailor‐made core–double‐shell structured nanoparticles. Subsequently, the film biomaterials combine to construct an ordered, dense bulk material by stacking‐up and hot‐pressing techniques. Surprisingly, the solid‐state supercapacitor based on compacted bulk material shows an ultrahigh energy density of 25.8 Wh kg−1, which is much higher than those previously reported advanced materials. Notably, the bulk material also demonstrates long‐term cycling stability, which can be maintained under ambient condition or immersed in H2SO4 electrolyte for more than 120 days. Thus, this research improves the competitiveness of protein‐based materials for real‐world applications such as flexible electronics and solid‐state supercapacitors.
Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co3O4 during Water Electrolysis via In Situ Spectroelectrochemical Techniques
Authors: Tran‐Phu Thanh , Chatti Manjunath , Leverett Joshua , Nguyen Thi Kim Anh , Simondson Darcy , Hoogeveen Dijon A , Kiy Alexander , Duong The , Johannessen Bernt , Meilak Jaydon , Kluth Patrick , Amal Rose , Simonov Alexandr N. , Hocking Rosalie K. , Daiyan Rahman , Tricoli Antonio
Published: March 2023

Unlocking the potential of the hydrogen economy is dependent on achieving green hydrogen (H2) production at competitive costs. Engineering highly active and durable catalysts for both oxygen and hydrogen evolution reactions (OER and HER) from earth‐abundant elements is key to decreasing costs of electrolysis, a carbon‐free route for H2 production. Here, a scalable strategy to prepare doped cobalt oxide (Co3O4) electrocatalysts with ultralow loading, disclosing the role of tungsten (W), molybdenum (Mo), and antimony (Sb) dopants in enhancing OER/HER activity in alkaline conditions, is reported. In situ Raman and X‐ray absorption spectroscopies, and electrochemical measurements demonstrate that the dopants do not alter the reaction mechanisms but increase the bulk conductivity and density of redox active sites. As a result, the W‐doped Co3O4 electrode requires ≈390 and ≈560 mV overpotentials to reach ±10 and ±100 mA cm−2 for OER and HER, respectively, over long‐term electrolysis. Furthermore, optimal Mo‐doping leads to the highest OER and HER activities of 8524 and 634 A g−1 at overpotentials of 0.67 and 0.45 V, respectively. These novel insights provide directions for the effective engineering of Co3O4 as a low‐cost material for green hydrogen electrocatalysis at large scales.
Metal‐Organic Framework Materials in Perovskite Solar Cells: Recent Advancements and Perspectives
Authors: Ye Yuxuan , Yin Yongqi , Chen Yan , Li Shuang , Li Lin , Yamauchi Yusuke
Published: March 2023

Organic–inorganic hybrid perovskite solar cells (PSCs) are among the most promising candidates for the next generation of photovoltaic devices because of the significant increase in their power conversion efficiency (PCE) from less than 10% to 25.7% in past decade. The metal‐organic framework (MOF) materials owing to their unique properties, such as large specific surface area, abundant binding sites, adjustable nanostructures, and synergistic effects, are used as additives or functional layers to enhance the device performance and long‐term stability of PSCs. This review focuses on the recent advancements in the applications of MOFs as/in different functional layers of PSCs. The photovoltaic performance, impact, and advantages of MOF materials integrated into the perovskite absorber, electron transport layer, hole transport layer, and interfacial layer are reviewed. In addition, the applicability of MOFs to mitigate leakage of Pb2+ from halide perovskites and corresponding devices is discussed. This review concludes with the perspectives on further research directions for employing MOFs in PSCs.
Thyroid‐Friendly Soft Materials as 3D Cell Culture Tool for Stimulating Thyroid Cell Function
Authors: Jun Indong , Cho Hyunki , Amos Sebastian E. , Choi Youngjun , Choi Yu Suk , Ryu Chang Seon , Lee Sang‐Ah , Han Dong‐Wook , Han Hyung‐Seop , Yang Ji Hun , Jeong Hyun‐Woo , Park Honghyun , Kim Young Jun
Published: March 2023

The disruption of thyroid hormones because of chemical exposure is a significant societal problem. Chemical evaluations of environmental and human health risks are conventionally based on animal experiments. However, owing to recent breakthroughs in biotechnology, the potential toxicity of chemicals can now be evaluated using 3D cell cultures. In this study, the interactive effects of thyroid‐friendly soft (TS) microspheres on thyroid cell aggregates are elucidated and their potential as a reliable toxicity assessment tool is evaluated. Using state‐of‐the‐art characterization methods coupled with cell‐based analysis and quadrupole time‐of‐flight mass spectrometry, it is shown that TS‐microsphere‐integrated thyroid cell aggregates exhibit improved thyroid function. Specifically, the responses of zebrafish embryos, which are used for thyroid toxicity analysis, and the TS‐microsphere‐integrated cell aggregates to methimazole (MMI), a known thyroid inhibitor, are compared. The results show that the thyroid hormone disruption response of the TS‐microsphere‐integrated thyroid cell aggregates to MMI is more sensitive compared with those of the zebrafish embryos and conventionally formed cell aggregates. This proof‐of‐concept approach can be used to control cellular function in the desired direction and hence evaluate thyroid function. Thus, the proposed TS‐microsphere‐integrated cell aggregates may yield new fundamental insights for advancing in vitro cell‐based research.
Imparting Outstanding Dispersibility to Nanoscaled 2D COFs for Constructing Organic Solvent Forward Osmosis Membranes
Authors: Chen Li , Zhou Cailong , Yang Tianyi , Zhou Wei , Chen Ying , Wang Linghao , Lu Chenyang , Dong Lichun
Published: March 2023

In the context of thin‐film nanocomposite membranes with interlayer (TFNi), nanoparticles are deposited uniformly onto the support prior to the formation of the polyamide (PA) layer. The successful implementation of this approach relies on the ability of nanoparticles to meet strict requirements regarding their sizes, dispersibility, and compatibility. Nevertheless, the synthesis of covalent organic frameworks (COFs) that are well‐dispersed, uniformly morphological, and exhibit improved affinity to the PA network, while preventing agglomeration, remains a significant challenge. In this work, a simple and efficient method is presented for the synthesis of well‐dispersed, uniformly morphological, and amine‐functionalized 2D imine‐linked COFs regardless of the ligand composition, group type, or framework pore size, by utilizing a polyethyleneimine (PEI) shielded covalent self‐assembly strategy. Subsequently, the as‐prepared COFs are incorporated into TFNi for the recycling of pharmaceutical synthetic organic solvents. After optimization, the membrane exhibits a high rejection rate and a favorable solvent flux, making it a reliable method for efficient organic recovery and the concentration of active pharmaceutical ingredient (API) from the mother liquor through an organic solvent forward osmosis (OSFO) process. Notably, this study represents the first investigation of the impact of COF nanoparticles in TFNi on OSFO performance.
Optimizing d‐Orbital Electronic Configuration via Metal–Metal Oxide Core–Shell Charge Donation for Boosting Reversible Oxygen Electrocatalysis
Authors: Wu Wei , chen Runzhe , Chen Suhao , Wang Zichen , Cheng Niancai
Published: March 2023

Tuning the d‐orbital electronic configuration of active sites to achieve well‐optimized adsorption strength of oxygen‐containing intermediates toward reversible oxygen electrocatalysis is desirable for efficient rechargeable Zn‐Air batteries but extremely challenging. Herein, this work proposes to construct a Co@Co3O4 core–shell structure to regulate the d‐orbital electronic configuration of Co3O4 for the enhanced bifunctional oxygen electrocatalysis. Theoretical calculations first evidence that electron donation from Co core to Co3O4 shell could downshift the d‐band center and simultaneously weak spin state of Co3O4, result in the well‐optimized adsorption strength of oxygen‐containing intermediates on Co3O4, thus contributing a favor way for oxygen reduction/evolution reaction (ORR/OER) bifunctional catalysis. As a proof‐of‐concept, the Co@Co3O4 embedded in Co, N co‐doped porous carbon derived from thickness controlled 2D metal‐organic‐framework is designed to realize the structure of computational prediction and further improve the performance. The optimized 15Co@Co3O4/PNC catalyst exhibits the superior bifunctional oxygen electrocatalytic activity with a small potential gap of 0.69 V and a peak power density of 158.5 mW cm−2 in ZABs. Moreover, DFT calculations shows that the more oxygen vacancies on Co3O4 contribute too strong adsorption of oxygen intermediates which limit the bifunctional electrocatalysis, while electron donation in the core–shell structure can alleviate the negative effect and maintain superior bifunctional overpotential.
Self‐Assembled Tetratic Crystals by Orthogonal Colloidal Force
Authors: Li Shanshan , He Jingwen , Qiao Shuoyuan , Zhang Xinghua , Liu Bing
Published: March 2023

Bonding simple building blocks to create crystalline materials with design has been sophisticated in the molecular world, but this is still very challenging for anisotropic nanoparticles or colloids, because the particle arrangements, including position and orientation, cannot be manipulated as expected. Here biconcave polystyrene (PS) discs to present a shape self‐recognition route are used, which can control both the position and orientation of particles during self‐assembly by directional colloidal forces. An unusual but very challenging two‐dimensional (2D) open superstructure—tetratic crystal (TC)—is achieved. The optical properties of the 2D TCs are studied by the finite difference time domain method, showing that the PS/Ag binary TC can be used to modulate the polarization state of the incident light, for example, converting the linearly polarized light into left‐handed or right‐handed circularly polarized light. This work paves an important way for self‐assembling many unprecedented crystalline materials.
The Role of Interfacial Water in CO2 Electrolysis over Ni‐N‐C Catalyst in a Membrane Electrode Assembly Electrolyzer
Authors: Wei Pengfei , Li Hefei , Li Rongtan , Wang Yi , Liu Tianfu , Cai Rui , Gao Dunfeng , Wang Guoxiong , Bao Xinhe
Published: March 2023

CO2 electrolysis is a promising route for achieving net‐zero emission through decarbonization. To realize CO2 electrolysis toward practical application, beyond catalyst structures, it is also critical to rationally manipulate catalyst microenvironments such as the water at the electrode/electrolyte interface. Here, the role of interfacial water in CO2 electrolysis over Ni‐N‐C catalyst modified with different polymers is investigated. Benefiting from a hydrophilic electrode/electrolyte interface, the Ni‐N‐C catalyst modified with quaternary ammonia poly(N‐methyl‐piperidine‐co‐p‐terphenyl) shows a Faradaic efficiency of 95% and a partial current density of 665 mA cm−2 for CO production in an alkaline membrane electrode assembly electrolyzer. A scale‐up demonstration using a 100 cm2 electrolyzer achieves a CO production rate of 514 mL min−1 at a current of 80 A. In‐situ microscopy and spectroscopy measurements indicate that the hydrophilic interface significantly promotes the formation of the *COOH intermediate, rationalizing the high CO2 electrolysis performance.
One‐Dimensional Chiral Copper Iodide Chain‐Like Structure Cu4I4(R/S‐3‐quinuclidinol)3 with Near‐Unity Photoluminescence Quantum Yield and Efficient Circularly Polarized Luminescence
Authors: Chen Jian , Pan Xin , Zhang Xuanyu , Sun Chen , Chen Congcong , Ji Xiaoqin , Chen Rui , Mao Lingling
Published: March 2023

Chiral organic−inorganic hybrid metal halide materials have shown great potential for circularly polarized luminescence (CPL) related applications for their tunable structures and efficient emissions. Here, this work combines the highly emissive Cu4I4 cubane cluster with chiral organic ligand R/S‐3‐quinuclidinol, to construct a new type of 1D Cu‐I chains, namely Cu4I4(R/S‐3‐quinuclidinol)3, crystallizing in noncentrosymmetric monoclinic P21 space group. These enantiomorphic hybrids exhibit long‐term stability and show bright yellow emission with a photoluminescence quantum yield (PLQY) close to 100%. Due to the successful chirality transfer from the chiral ligands to the inorganic backbone, the enantiomers show intriguing chiroptical properties, such as circular dichroism (CD) and CPL. The CPL dissymmetry factor (glum) is measured to be ≈4 × 10−3. Time‐resolved photoluminescence (PL) measurements show long averaged decay lifetime up to 10 µs. The structural details within the Cu4I4 reveal the chiral nature of these basic building units, which are significantly different than in the achiral case. This discovery provides new structural insights for the design of high performance CPL materials and their applications in light emitting devices.
Development of a ZIF‐91‐Porous‐Liquid‐Based Composite Hydrogel Dressing System for Diabetic Wound Healing
Authors: Weng Puxin , Liu Kun , Yuan Meng , Huang Guo‐Quan , Wu Kun , Yang Xiaofan , Dai Honglian , Lu Weigang , Li Dan
Published: March 2023

Porous metal–organic framework (MOF) liquids with permanent porosity, good fluidity, and fine dispersion attract broad attention in catalysis, transportation, gas storage, and chemical separations. Yet, the design and synthesis of porous MOF liquids for drug delivery remain less explored. Herein, a simple and general strategy is reported to prepare ZIF‐91 porous liquid (ZIF‐91‐PL) via surface modification and ion exchange. The cationic nature of ZIF‐91‐PL not only renders it antibacterial but also with high curcumin loading capacity and sustained release. More importantly, the acrylate group on the grafted side chain of ZIF‐91‐PL makes it feasible to crosslink with modified gelatin through light curing, and the obtained hydrogel shows a significantly improved healing effect on the wound of diabetes. This work demonstrates for the first time, a MOF‐based porous liquid for drug delivery, and the further fabrication of composite hydrogel may have potential applications in biomedical science.
Moisture‐Enabled Germination of Heat‐Activated Bacillus Endospores for Rapid and Practical Bioelectricity Generation: Toward Portable, Storable Bacteria‐Powered Biobatteries
Authors: Rezaie Maryam , Choi Seokheun
Published: March 2023

Small‐scale battery‐like microbial fuel cells (MFCs) are a promising alternative power source for future low‐power electronics. Controllable microbial electrocatalytic activity in a miniaturized MFC with unlimited biodegradable energy resources would enable simple power generation in various environmental settings. However, the short shelf‐life of living biocatalysts, few ways to activate the stored biocatalysts, and extremely low electrocatalytic capabilities render the miniature MFCs unsuitable for practical use. Here, heat‐activated Bacillus subtilis spores are revolutionarily used as a dormant biocatalyst that can survive storage and rapidly germinate when exposed to special nutrients that are preloaded in the device. A microporous, graphene hydrogel allows the adsorption of moisture from the air, moves the nutrients to the spores, and triggers their germination for power generation. In particular, forming a CuO–hydrogel anode and an Ag2O–hydrogel cathode promotes superior electrocatalytic activities leading to an exceptionally high electrical performance in the MFC. The battery‐type MFC device is readily activated by moisture harvesting, producing a maximum power density of 0.4 mW cm−2 and a maximum current density of 2.2 mA cm−2. The MFC configuration is readily stackable in series and a three‐MFC pack produces enough power for several low‐power applications, demonstrating its practical feasibility as a sole power source.
Pre‐Induced ICD Membrane‐Coated Carrier‐Free Nanoparticles for the Personalized Lung Cancer Immunotherapy
Authors: Li Shilin , Jiang Shasha , Rahman Muhammad Saif Ur , Mei Jie , Wang Xinlian , Jiang Jipeng , Chen Yandong , Xu Shanshan , Liu Ying
Published: March 2023

Immunotherapy is a required adjuvant method in lung cancer therapy clinically. The single immune adjuvant failed to show the expected clinical therapeutic efficacy due to its rapid drug metabolism and inability to accumulate in the tumor site efficiently. Immunogenic cell death (ICD) is a new anti‐tumor strategy combined with immune adjuvants. It can provide tumor‐associated antigens, activate dendritic cells, and attract lymphoid T cells into the tumor microenvironment. Here doxorubicin‐induced tumor membrane‐coated iron (II)‐cytosine‐phosphate‐guanine nanoparticles (DM@NPs) are shown for efficient co‐delivery of tumor‐associated antigens and adjuvant. Higher expression of ICD‐related membrane proteins on the surface of the DM@NPs leads to the enhanced uptake of DM@NPs by dendritic cells (DCs), thereby promoting the DCs maturation and pro‐inflammatory cytokines release. DM@NPs can remarkably increase the T cell infiltrations, remodel the tumor immune microenvironment and inhibit tumor progression in vivo. These findings reveal that pre‐induced ICD tumor cell membrane‐encapsulated nanoparticles can enhance immunotherapy responses and provide an effective biomimetic nanomaterial‐based therapeutic strategy for lung cancer.
Integration of Self‐Passivated Topological Electrodes for Advanced 2D Optoelectronic Devices
Authors: Huang Zihao , Luo Zhongtong , Deng Ziwen , Yang Mengmeng , Gao Wei , Yao Jiandong , Zhao Yu , Dong Huafeng , Zheng Zhaoqiang , Li Jingbo
Published: March 2023

With the rapid development of two‐dimensional semiconductor technology, the inevitable chemical disorder at a typical metal–semiconductor interface has become an increasingly serious problem that degrades the performance of 2D semiconductor optoelectronic devices. Herein, defect‐free van der Waals contacts have been achieved by utilizing topological Bi2Se3 as the electrodes. Such clean and atomically sharp contacts avoid the consumption of photogenerated carriers at the interface, enabling a markedly boosted sensitivity as compared to counterpart devices with directly deposited metal electrodes. Typically, the device with 2D WSe2 channel realizes a high responsivity of 20.5 A W−1, an excellent detectivity of 2.18 × 1012 Jones, and a fast rise/decay time of 41.66/38.81 ms. Furthermore, high‐resolution visible‐light imaging capability of the WSe2 device is demonstrated, indicating its promising application prospect in future optoelectronic systems. More inspiringly, the topological electrodes are universally applicable to other 2D semiconductor channels, including WS2 and InSe, suggesting its broad applicability. These results open fascinating opportunities for the development of high‐performance electronics and optoelectronics.
Near‐Infrared Trapping by Surface Plasmons in Randomized Platinum–Ceramic Metamaterial for Thermal Barrier Coatings
Authors: Yang Zesheng , Huang Muzhang , Yang Ronggui , Sun Jingbo , Zhang Xuefei , Pan Wei , Wan Chunlei
Published: March 2023

As the operation temperature of next generation gas turbine is targeted to be 1800 °C toward a higher efficiency and lower carbon emission, the near‐infrared (NIR) thermal radiation becomes a major concern for the durability of the metallic turbine blades. Although thermal barrier coatings (TBCs) are applied to provide thermal insulations, they are translucent to the NIR radiation. It is a major challenge for TBCs to achieve optically thick with limited physical thickness (usually < 1 mm) for effectively shielding the NIR radiation damage. Here, an NIR metamaterial is reported, where a Gd2Zr2O7 ceramic matrix is randomly dispersed with microscale Pt (0.53 vol%) nanoparticles with a size of 100–500 nm. Attenuated by the Gd2Zr2O7 matrix, a broadband NIR extinction is achieved through the red‐shifted plasmon resonance frequencies and higher‐order multipole resonances of the Pt nanoparticles. A very high absorption coefficient of ≈3 × 104 m−1, approaching the Rosseland diffusion limit for a typical coating thickness, minimizes the radiative thermal conductivity to ≈10−2 W m−1 K−1 and successfully shields the radiative heat transfer. This work suggests that constructing a conductor/ceramic metamaterial with tunable plasmonics could be a strategy to shield NIR thermal radiation for high temperature applications.
Pathway to the Polyvinyl‐Acetate‐Assisted PEDOT:PSS as a Dopant‐Free Hole Transporting Material in Planar Heterojunction Perovskite Solar Cells
Authors: Kim Jihyun , Park Byungwoo , Chung Daewon , Kim Jinhyun
Published: March 2023

To achieve world's burgeoning appetite in obtaining high‐energy conversion efficiency, not only perovskite semiconductor but also hole transporting material (HTM) takes a significant role as a game changer. The dopant of conventional organic HTM induces side effects of degradation, and inorganic HTM reacts or penetrates with the underlying perovskite layer. Considering those issues, poly(3,4‐ethylenedioxythiophene:poly(styrene sulfonate) (PEDOT:PSS) as an alternative HTM has been explored in the field of perovskite solar cells with its outstanding hole transporting property. Herein, incorporation of polyvinyl acetate (PVAc) in PEDOT:PSS paves the way to wide applications in device structural perspective, as to say, in n–i–p structure. The presence of the ester group in PVAc donates the bonding site to the perovskite layer, which improves the adhesion, resulting in enhanced charge transport ability as well as device stability. PVAc‐treated PEDOT:PSS device exhibited 20% higher power conversion efficiency (PCE) than the PVAc‐free device and retained 80% of initial PCE after 1000 h under extreme conditions (AM 1.5G and 60 °C).
Anisotropic Charge Transport in Cu(In,Ga)Se2 by Heavy Alkali Postdeposition Treatment for Reducing Cell‐to‐Module Efficiency Loss in Monolithically Integrated Photovoltaic Modules
Authors: Yu Hyeonggeun , Choi Eun Pyung , Chai Sung Uk , Lee Sang hyo , Park Ha Kyung , Kim Gee Yeong , Jo William , Kim Won Mok , Kim Donghwan , Ju Byeong-Kwon , Min Byoung Koun , Jeong Jeung-hyun
Published: March 2023

The recent efficiency boosting of Cu(In,Ga)Se2 (CIGS) solar cells is undoubtedly triggered by heavy alkali postdeposition treatments (PDTs). However, the effects are not obvious under monolithically integrated CIGS modules where various current‐shunting sources can deteriorate the device performance. Herein, It is reported that KF PDT can effectively suppress the major shunting sources caused by P1 and P3 laser scribing for monolithic interconnection, reducing the cell‐to‐module (CTM) efficiency gap in CIGS photovoltaics. CIGS with NaF PDT exhibits nearly isotropic and high hole mobilities, causing a large CTM efficiency loss. CIGS with additional KF PDT, on the other hand, reveals much lower in‐plane hole mobility than the out‐of‐plane component, significantly increasing the P1 shunt resistance without exacerbating the photocarrier extraction in the active area. It is suggested that such anisotropic charge transport is due to carrier scattering by low‐conductivity phases at the CIGS grain boundaries. Furthermore, passivation of the front junction by KF PDT raises the tolerance to P3 scribing‐induced damage, increasing the P3 shunt resistance while preserving the junction property unlike the NaF PDT case. The work implies that the recent trend of employing heavy alkali PDTs for a high‐efficiency cell is also crucial for designing a high‐efficiency CIGS module.
Crack Initiation Mechanism of AISI 4340 Steel for High‐Cycle Torsional Fatigue Loading
Authors: Xu Zikuan , Wang Bin , Zhang Peng , Zhu Yankun , Wang Xuegang , Zhang Zhefeng
Published: March 2023

The nucleation of microstructural fatigue cracks in AISI 4340 steel is investigated. The pre‐electropolished specimen is employed for the observation of the very early stage of fatigue crack initiation correlated with the microstructure. It is found that there are precipitate‐free zones (PFZs) around the lath and packet boundary, and the strength of PFZ is lower than that of the lath due to the lack of second‐phase strengthening. Therefore, the fatigue crack would first initiate within the PFZ. Besides, the initiated crack plane usually is the maximum shear stress plane. However, the MnS inclusions would cause stress concentration so that the lath boundary (LB) deviating from the maximum shear stress plane could also have sufficient driving force to crack. In contrast, when the LB is vertical to the cracked MnS inclusion, it would prevent the crack from propagating into the matrix because of the anisotropy of lath martensite. The effects of the stress concentration caused by the MnS inclusion on the maximum deviation angle and the S‐N curve are discussed.
New observing strategies testbed: A digital prototyping platform for distributed space missions
Authors: Chell Brian , LeVine Matthew J. , Capra Leigha , Sellers Jerry J. , Grogan Paul T.
Published: March 2023

The New Observing Strategies Testbed (NOS‐T) is a digital engineering environment for enabling distributed space mission (DSM) technology demonstrations. Its event‐driven architecture enables users to orchestrate DSM test campaigns by developing applications that communicate state changes via messages. NOS‐T is motivated by requirements such as geographical distribution, cross‐boundary participation, wide applicability, and usability that make it unique in this field. This article introduces NOS‐T and describes its architecture in the context of an example DSM test suite, FireSat+. The scalability of NOS‐T is demonstrated with a performance assessment of its capabilities under a stress test of high message frequency and payload size, which are both related to the complexity of potential user‐generated test cases. Results show that message periodicity has no significant effect on median delay time over the ranges sampled; however, the message payload size induces linear growth in median delay time of approximately 1.5 ms per kB. Future NOS‐T applications can adjust the execution time scaling factor and message payload size to match operational constraints on allowable delay.
Toward decolonizingSTEM: Centering place and sense of place forcommunity‐based problem‐solving
Authors: O'Neill Tara , Finau‐Faumuina Bella Melenaite , Ford Tessie Uʻilani Lumabao
Published: March 2023

Given the growing global environmental threats, shifts to increasingly binary thinking that isolate and polarize discourse, and the erosion of caring for each other and our places, the authors believe it is imperative that we change the way science and science, technology, engineering, and math (STEM) education connect with communities and are taught in school. As part of the larger study, this paper explores how the integration of STEMS2Pedagogy with community based problem solving (re)shapes two case‐study teachers' learning environments and serves as a tool to facilitate decolonizing STEM education by addressing the research question. Research question: How does the integration of community‐based problem‐solving and STEMS2Pedagogy impact how the case study teachers think about STEM education and the design of STEM curriculum? Drawing from longitudinal critical ethnographic case studies and Hawaiian hermeneutics frameworks, two public school educators (co‐authors), we collected data between Fall 2017 to Fall 2021. The inductive analysis process described above resulted in two key claims: (1) Grounding STEM instruction in place strengthens sense of place and kuleana, and (2) Strengthening one's sense ofkuleanachanges the measure of success.
Colorectal polyps: Targets for fluorescence‐guided endoscopy to detect high‐grade dysplasia and T1 colorectal cancer
Authors: Dekkers Nik , Zonoobi Elham , Dang Hao , Warmerdam Mats I. , Crobach Stijn , Langers Alexandra M. J. , van der Kraan Jolein , Hilling Denise E. , Peeters Koen C. M. J. , Holman Fabian A. , Vahrmeijer Alexander L. , Sier Cornelis F. M. , Hardwick James C. H. , Boonstra Jurjen J.
Published: March 2023

Background

Differentiating high‐grade dysplasia (HGD) and T1 colorectal cancer (T1CRC) from low‐grade dysplasia (LGD) in colorectal polyps can be challenging. Incorrect recognition of HGD or T1CRC foci can lead to a need for additional treatment after local resection, which might not have been necessary if it was recognized correctly. Tumor‐targeted fluorescence‐guided endoscopy might help to improve recognition.

Objective

Selecting the most suitable HGD and T1CRC‐specific imaging target from a panel of well‐established biomarkers: carcinoembryonic antigen (CEA), c‐mesenchymal‐epithelial transition factor (c‐MET), epithelial cell adhesion molecule (EpCAM), folate receptor alpha (FRα), and integrin alpha‐v beta‐6 (αvβ6).

Methods

En bloc resection specimens of colorectal polyps harboring HGD or T1CRC were selected. Immunohistochemistry on paraffin sections was used to determine the biomarker expression in normal epithelium, LGD, HGD, and T1CRC (scores of 0–12). The differential expression in HGD‐T1CRC components compared to surrounding LGD and normal components was assessed, just as the sensitivity and specificity of each marker.

Results

60 specimens were included (21 HGD, 39 T1CRC). Positive expression (score >1) of HGD‐T1CRC components was found in 73.3%, 78.3%, and 100% of cases for CEA, c‐MET, and EpCAM, respectively, and in <40% for FRα and αvβ6. Negative expression (score 0–1) of the LGD component occurred more frequently for CEA (66.1%) than c‐MET (31.6%) and EpCAM (0%). The differential expression in the HGD‐T1CRC component compared to the surrounding LGD component was found for CEA in 66.7%, for c‐MET in 43.1%, for EpCAM in 17.2%, for FRα in 22.4%, and for αvβ6 in 15.5% of the cases. Moreover, CEA showed the highest combined sensitivity (65.0%) and specificity (75.0%) for the detection of an HGD‐T1CRC component in colorectal polyps.

Conclusion

Of the tested targets, CEA appears the most suitable to specifically detect HGD and T1 cancer foci in colorectal polyps. An in vivo study using tumor‐targeted fluorescence‐guided endoscopy should confirm these findings.