bluuebunny/crossref_metadata_2025 huggingface dataset:
Permanently Mechanically Adjustable Photothermal Catalytic Spontaneous Double Cross‐Linking Network Enables Durable and Stretchable Plant Skin‐Like Materials
Authors: Zhai Wenxiang , Xu Min , Zhong Yijing , Zhang Kun , Li Jinming , Ding Kejiao , Wei Xinli , Cai Liping , Xia Changlei
Published: July 2023

In cellulose‐based plastics, as a type of thermoplastic and thermosetting materials, the excellent balance of mechanical strength and ductility poses a large challenge. To tackle this problem, a novel approach is devised to introduce reversible non‐covalent ester cross‐linking into dynamic covalent hydrogen‐bonded polymer networks. However, the formation of ester bonds typically requires excess reactants and dehydrating agents, which is energy‐intensive, environmentally harmful, and costly. To address these concerns, inspired by polyester‐rich plant bark, a supramolecular composite material is developed. It can be dissolved and regenerated using a binary solvent system (choline hexanoate/choline chloride‐oxalic acid). In water, this supramolecular composite material underwent self‐healing and ester exchange reactions to form double‐cross‐linked networks, interfaced with photo‐thermal catalysis promoting the reaction due to its high photo‐thermal conversion efficiency (86.7%) and water evaporation rate (1.38 kg m−2 h−1). This enables the rapid and repeatable construction of durable and stretchable biomaterials. The mechanical properties of the supramolecular plastic can be adjusted by solar photo‐thermal conditions of the synthesis environment. These materials exhibit high performance in solar water evaporation and have self‐healing properties and are degradable, recyclable, and capable of eliminating their own adhesions.
Quasi‐1D Polymer Semiconductor–Diarylethene Blends: High Performance Optically Switchable Transistors
Authors: Chen Yusheng , Wang Hanlin , Chen Hu , Zhang Weimin , Xu Shunqi , Pätzel Michael , Ma Chun , Wang Cang , McCulloch Iain , Hecht Stefan , Samorì Paolo
Published: July 2023

Optically switchable field‐effect transistors (OSFETs) are non‐volatile photonic memory devices holding a great potential for applications in optical information storage and telecommunications. Solution processing of blends of photochromic molecules and π‐conjugated polymers is a low‐cost protocol to integrate simultaneously optical switching and charge transport functions in large‐area devices. However, the limited reversibility of the isomerization of photochromic molecules due to steric hindrance when embedded in ordered polymeric matrices represents a severe limitation and it obliges to incorporate as much as 20% in weight of the photochromic component, thereby drastically diluting the electronic function, limiting the device performance. Herein, a comparative study of the photoresponsivity of a suitably designed diarylethene molecule is reported when embedded in the matrix of six different polymer semiconductors displaying diverse charge transport properties. In particular, this study focuses on three semi‐crystalline polymers and three quasi‐1D polymers. It is found that 1% w/w of 1,2‐bis(5‐(3,5‐di‐tert‐butylphenyl)‐2‐methylthiophen‐3‐yl)cyclopent‐1‐ene in a blend with poly(indacenodithiophene‐co‐benzothiadiazole) is sufficient to fabricate OSFETs combining photo‐modulation efficiencies of 45.5%, mobilities >1 cm2 V−1s−1, and photo‐recovered efficiencies of 98.1%. These findings demonstrate that quasi‐1D polymer semiconductors, because of their charge transport dominated by intra‐molecular processes, epitomize the molecular design principles required for the fabrication of high‐performance OSFETs.
Self‐Discharge Behavior of Graphitic Cathodes for Rechargeable Aluminum Batteries
Authors: Li Chi , Chen Yi‐Xiu , Patra Jagabandhu , Lu Shi‐Xian , Hsieh Chien‐Te , Yang Chun‐Chen , Dong Quan‐Feng , Li Ju , Chang Jeng‐Kuei
Published: July 2023

Self‐discharge, which is associated with energy efficiency loss, is a critical issue that hinders practical applications of rechargeable aluminum batteries (RABs). The self‐discharge properties of two commonly‐used RAB positive electrode materials, namely natural graphite (NG) and expanded graphite (EG), are investigated in this work. EG, which has a wider spacing between graphitic layers and a larger surface area, has a higher self‐discharge rate than that of NG. After 12 h of rest, NG and EG electrodes retain 74% and 63% of their initial capacities, respectively, after charging up to 2.4 V at 0.3 A g−1. Operando X‐ray diffraction, X‐ray photoelectron spectroscopy, and energy‐dispersive X‐ray spectroscopy are employed to study the self‐discharge mechanism. The self‐discharge loss is related to the spontaneous deintercalation of AlCl4− anions from the graphite lattice charge‐compensated by Cl2 gas evolution at the same electrode and can be restored (i.e., no permanent damage is caused to the electrodes) in the next charge‐discharge cycle. It is found that the charging rate and depth of charge also affect the self‐discharge properties. In addition, the self‐discharge rates of NG in 1‐ethyl‐3‐methylimidazolium chloride–AlCl3 and urea–AlCl3 electrolytes are compared.
Broad‐Wavelength Light‐Driven High‐Speed Hybrid Crystal Actuators Actuated Inside Tissue‐Like Phantoms
Authors: Kim Dong Wook , Hagiwara Yuki , Hasebe Shodai , Dogan Nihal Olcay , Zhang Mingchao , Asahi Toru , Koshima Hideko , Sitti Metin
Published: July 2023

Research on molecular crystals exhibiting light‐driven actuation has made remarkable progress through the development of various molecules and the identification of driving mechanisms. However, crystals developed to date have been driven mainly by ultraviolet (UV) or blue light irradiation, and driving by red or near‐infrared (NIR) light has not been attempted yet. Herein, a broad‐wavelength light‐driven molecular crystals that exhibit high‐speed bending by photothermal effect is developed. Titanium carbide (Ti3C2Tx) MXene nanosheets are integrated into salicylideneaniline crystals to extend the wavelength range that causes photothermally driven bending to UV, visible, and NIR light. In addition, unlike the thin pristine molecular crystals that show slow photoisomerization‐induced bending only under UV light, the MXene layer enables the molecular crystals to be actuated rapidly regardless of their thickness over a wide range of wavelengths. The hybridization of molecular crystals with MXene, which exhibits strong biocompatibility as well as NIR light‐driven photothermal effect, allows for the bending of the hybrid crystals inside agar phantoms mimicking biological tissue. Last, it is confirmed that MXene hybridization can be extended to common molecular crystals including various salicylideneaniline and anisole derivatives.
Hierarchically Released Liquid Metal Nanoparticles for Mild Photothermal Therapy/Chemotherapy of Breast Cancer Bone Metastases via Remodeling Tumor Stromal Microenvironment
Authors: Shen Yaping , Zou Yang , Bie Binglin , Lv Yonggang
Published: July 2023

Currently, the treatment strategy for bone metastasis is mainly to inhibit the growth of tumor cells and the activity of osteoclasts, while ignoring the influence of the tumor stromal microenvironment (TSM) on the progression of bone metastasis. Herein, a dual‐target liquid metal (LM)‐based drug delivery system (DDS) with favorable photothermal performance is designed to spatially program the delivery of multiple therapeutic agents to enhance the treatment of bone metastasis through TSM remodeling. Briefly, mesoporous silicon‐coated LM is integrated into zeolitic imidazolate framework‐8 (ZIF‐8) with both bone‐seeking and tumor‐targeting capacities. Curcumin (Cur), a tumor microenvironment modulator, is encapsulated into ZIF‐8, and doxorubicin (DOX) is enclosed inside mesoporous silicon. Specific accumulation of the LM‐based DDS in bone metastases first relieves the tumor stroma by releasing Cur in response to the acidic tumor microenvironment and then releases DOX deep into the tumor under near‐infrared light irradiation. The combined strategy of the LM‐based DDS and mild photothermal therapy has been shown to effectively restrain cross‐talk between osteoclasts and tumor cells by inhibiting the secretion of transforming growth factor‐β, degrading extracellular matrix components, and increasing infiltration of CD4+ and CD8+ T cells, which provides a promising strategy for the treatment of bone metastases.
Reduced Graphene Oxide Electrolyte‐Gated Transistor Immunosensor with Highly Selective Multiparametric Detection of Anti‐Drug Antibodies
Authors: Sensi Matteo , de Oliveira Rafael Furlan , Berto Marcello , Palmieri Marina , Ruini Emilio , Livio Pietro Antonio , Conti Andrea , Pinti Marcello , Salvarani Carlo , Cossarizza Andrea , Cabot Joan M. , Ricart Jordi , Casalini Stefano , González‐García María Begoña , Fanjul‐Bolado Pablo , Bortolotti Carlo Augusto , Samorì Paolo , Biscarini Fabio
Published: July 2023

The advent of immunotherapies with biological drugs has revolutionized the treatment of cancers and auto‐immune diseases. However, in some patients, the production of anti‐drug antibodies (ADAs) hampers the drug efficacy. The concentration of ADAs is typically in the range of 1–10 pm; hence their immunodetection is challenging. ADAs toward Infliximab (IFX), a drug used to treat rheumatoid arthritis and other auto‐immune diseases, are focussed. An ambipolar electrolyte‐gated transistor (EGT) immunosensor is reported based on a reduced graphene oxide (rGO) channel and IFX bound to the gate electrode as the specific probe. The rGO‐EGTs are easy to fabricate and exhibit low voltage operations (≤ 0.3 V), a robust response within 15 min, and ultra‐high sensitivity (10 am limit of detection). A multiparametric analysis of the whole rGO‐EGT transfer curves based on the type‐I generalized extreme value distribution is proposed. It is demonstrated that it allows to selectively quantify ADAs also in the co‐presence of its antagonist tumor necrosis factor alpha (TNF‐α), the natural circulating target of IFX.
Recent Progress in Functional Nanomaterials towards the Storage, Separation, and Removal of Tritium
Authors: Rethinasabapathy Muruganantham , Ghoreishian Seyed Majid , Hwang Seung‐Kyu , Han Young‐Kyu , Roh Changhyun , Huh Yun Suk
Published: July 2023

Tritium is a sustainable next‐generation prime fuel for generating nuclear energy through fusion reactions to fulfill the increasing global energy demand. Owing to the scarcity–high demand tradeoff, tritium must be bred inside a fusion reactor to ensure sustainability and must therefore be separated from its isotopes (protium and deuterium) in pure form, stored safely, and supplied on demand. Existing multistage isotope separation technologies exhibit low separation efficiency and require intensive energy inputs and large capital investments. Furthermore, tritium‐contaminated heavy water constitutes a major fraction of nuclear waste, and accidents like the one at Fukushima Daiichi leave behind thousands of tons of diluted tritiated water, whose removal is beneficial from an environmental point of view. In this review, the recent progress and main research trends in hydrogen isotope storage and separation by focusing on the use of metal hydride (e.g., intermetallic, and high‐entropy alloys), porous (e.g., zeolites and metal organic frameworks (MOFs)), and 2‐D layered (e.g., graphene, hexagonal boron nitride (h‐BN), and MXenes) materials to separate and store tritium based on their diverse functionalities are discussed. Finally, the challenges and future directions for implementing tritium storage and separation are summarized in the reviewed materials.
A Nano‐Biohybrid‐Based Bio‐Solar Cell to Regulate the Electrical Signal Transmission to Living Cells for Biomedical Application
Authors: Lim Joungpyo , Shin Minkyu , Ha Taehyung , Su Wei Wen , Yoon Jinho , Choi Jeong‐Woo
Published: July 2023

Bio‐solar cells are studied as sustainable and biocompatible energy sources with significant potential for biomedical applications. However, they are composed of light‐harvesting biomolecules with narrow absorption wavelengths and weak transient photocurrent generation. In this study, a nano‐biohybrid‐based bio‐solar cell composed of bacteriorhodopsin, chlorophyllin, and Ni/TiO2 nanoparticles is developed to overcome the current limitations and verify the possibility of biomedical applications. Bacteriorhodopsin and chlorophyllin are introduced as light‐harvesting biomolecules to broaden the absorption wavelength. As a photocatalyst, Ni/TiO2 nanoparticles are introduced to generate a photocurrent and amplify the photocurrent generated by the biomolecules. The developed bio‐solar cell absorbs a broad range of visible wavelengths and generates an amplified stationary photocurrent density (152.6 nA cm−2) with a long lifetime (up to 1 month). Besides, the electrophysiological signals of muscle cells at neuromuscular junctions are precisely regulated by motor neurons excited by the photocurrent of the bio‐solar cell, indicating that the bio‐solar cell can control living cells by signal transmission through other types of living cells. The proposed nano‐biohybrid‐based bio‐solar cell can be used as a sustainable and biocompatible energy source for the development of wearable and implantable biodevices and bioelectronic medicines for humans.
Phase Engineering of 2D Spinel‐Type Manganese Oxides
Authors: Feng Xiaoqiang , Zhai Baoxing , Cheng Ruiqing , Yin Lei , Wen Yao , Jiang Jian , Wang Hao , Li Zhongwei , Zhu Yushan , He Jun
Published: July 2023

2D magnetic materials have been of interest due to their unique long‐range magnetic ordering in the low‐dimensional regime and potential applications in spintronics. Currently, most studies are focused on strippable van der Waals magnetic materials with layered structures, which typically suffer from a poor stability and scarce species. Spinel oxides have a good environmental stability and rich magnetic properties. However, the isotropic bonding and close‐packed nonlayered crystal structure make their 2D growth challenging, let alone the phase engineering. Herein, a phase‐controllable synthesis of 2D single‐crystalline spinel‐type oxides is reported. Using the van der Waals epitaxy strategy, the thicknesses of the obtained tetragonal and hexagonal manganese oxide (Mn3O4) nanosheets can be tuned down to 7.1 nm and one unit cell (0.7 nm), respectively. The magnetic properties of these two phases are evaluated using vibrating‐sample magnetometry and first‐principle calculations. Both structures exhibit a Curie temperature of 48 K. Owing to its ultrathin geometry, the Mn3O4 nanosheet exhibits a superior ultraviolet detection performance with an ultralow noise power density of 0.126 pA Hz−1/2. This study broadens the range of 2D magnetic semiconductors and highlights their potential applications in future information devices.
Doping Engineering to Modulate Lattice and Electronic Structure for Enhanced Piezocatalytic Therapy and Ferroptosis
Authors: Tian Boshi , Tian Ruixue , Liu Shaohua , Wang Yan , Gai Shili , Xie Ying , Yang Dan , He Fei , Yang Piaoping , Lin Jun
Published: July 2023

Piezocatalytic therapy, which generates reactive oxygen species (ROS) under mechanical force, has garnered extensive attention for its use in cancer therapy owing to its deep tissue penetration depth and less O2‐dependence. However, the piezocatalytic therapeutic efficiency is limited owing to the poor piezoresponse, low separation of electron–hole pairs, and complicated tumor microenvironment (TME). Herein, a biodegradable, porous Mn‐doped ZnO (Mn–ZnO) nanocluster with enhanced piezoelectric effect is constructed via doping engineering. Mn‐doping not only induces lattice distortion to increase polarization but also creates rich oxygen vacancies (OV) for suppressing the recombination of electron–hole pairs, leading to high‐efficiency generation of ROS under ultrasound irradiation. Moreover, Mn‐doped ZnO shows TME‐responsive multienzyme‐mimicking activity and glutathione (GSH) depletion ability owing to the mixed valence of Mn (II/III), further aggravating oxidative stress. Density functional theory calculations show that Mn‐doping can improve the piezocatalytic performance and enzyme activity of Mn–ZnO due to the presence of OV. Benefiting from the boosting of ROS generation and GSH depletion ability, Mn–ZnO can significantly accelerate the accumulation of lipid peroxide and inactivate glutathione peroxidase 4 (GPX4) to induce ferroptosis. The work may provide new guidance for exploring novel piezoelectric sonosensitizers for tumor therapy.
The Oxygen Evolution Reaction Drives Passivity Breakdown for Ni–Cr–Mo Alloys
Authors: Larsson Alfred , Grespi Andrea , Abbondanza Giuseppe , Eidhagen Josefin , Gajdek Dorotea , Simonov Konstantin , Yue Xiaoqi , Lienert Ulrich , Hegedüs Zoltan , Jeromin Arno , Keller Thomas F. , Scardamaglia Mattia , Shavorskiy Andrey , Merte Lindsay R. , Pan Jinshan , Lundgren Edvin
Published: July 2023

Corrosion is the main factor limiting the lifetime of metallic materials, and a fundamental understanding of the governing mechanism and surface processes is difficult to achieve since the thin oxide films at the metal–liquid interface governing passivity are notoriously challenging to study. In this work, a combination of synchrotron‐based techniques and electrochemical methods is used to investigate the passive film breakdown of a Ni–Cr–Mo alloy, which is used in many industrial applications. This alloy is found to be active toward oxygen evolution reaction (OER), and the OER onset coincides with the loss of passivity and severe metal dissolution. The OER mechanism involves the oxidation of Mo4+ sites in the oxide film to Mo6+ that can be dissolved, which results in passivity breakdown. This is fundamentally different from typical transpassive breakdown of Cr‐containing alloys where Cr6+ is postulated to be dissolved at high anodic potentials, which is not observed here. At high current densities, OER also leads to acidification of the solution near the surface, further triggering metal dissolution. The OER plays an important role in the mechanism of passivity breakdown of Ni–Cr–Mo alloys due to their catalytic activity, and this effect needs to be considered when studying the corrosion of catalytically active alloys.
A Sodiophilic Amyloid Fibril Modified Separator for Dendrite‐Free Sodium‐Metal Batteries
Authors: Wang Jinming , Gao Yan , Liu Di , Zou Guodong , Li Lanjie , Fernandez Carlos , Zhang Qingrui , Peng Qiuming
Published: July 2023

Sodium (Na) batteries are being considered as prospective candidates for the next generation of secondary batteries in contrast to lithium‐based batteries, due to their high raw‐material abundance, low cost, and sustainability. However, the unfavorable growth of Na‐metal deposition and severe interfacial reactions have prevented their large‐scale applications. Here, a vacuum filtration strategy, through amyloid‐fibril‐modified glass‐fiber separators, is proposed to address these issues. The modified symmetric cell can be cycled for 1800 h, surpassing the performance of previously reported Na‐based electrodes under an ester‐based electrolyte. Moreover, the Na/Na3V2(PO4)3 full cell with a sodiophilic amyloid‐fibril‐modified separator exhibits a capacity retention of 87.13% even after 1000 cycles. Both the experimental and the theoretical results show that the sodiophilic amyloid fibril homogenizes the electric field and Na‐ion concentration, fundamentally inhibiting dendrite formation. Simultaneously, the glutamine amino acids in the amyloid fibril have the highest adsorption energy for Na, resulting in the formation of a stable Na3N‐ and NaNxOy‐rich solid‐electrolyte‐interface film on the anode during cycling. This work provides not only a possible pathway to solve the dendrite problem in metal batteries using environmentally friendly biomacromolecular materials, but also a new direction for expanding biomaterial applications.
Lanthanide‐Functionalized Water‐Soluble Ionic Motors: Synergetically Regulated Rotary Motion by Allostery and Triplet Sensitization
Authors: Li Shaorui , Zhao Yuanmeng , Li Quan , Li Menglian , Zhang Xu , Xu Hai‐Bing
Published: July 2023

Molecular motors, based on overcrowded alkenes (L) serving as ligands to chelate lanthanide nitrate, afford the first lanthanide‐functionalized water‐soluble ionic compound [L2‐Ln(NO3)2(H2O)2]·NO3 (LnL2). Benefitting from the “pull–push” feature of L together with 3LMCT from L to LnIII, irradiation with visible light not only drives photochemical isomerization but also induces energy transfer from L to LnIII, decreasing their intensity of low‐energy 3LMCT (ligand‐to‐metal triplet energy transfer) absorptions and sensitizing the Ln‐based luminescence. Thus, the typical EuIII‐based luminescence of EuL2 favors tracing its movement by time‐resolved luminescence, and temperature‐dependent luminescence renders it possibly to be used as potential luminescent thermometers. Very excitingly, besides a contraction of the stator by Ln–L interactions on decreasing the steric hindrance on the “fjord region,” the efficiency of intramolecular 3LMCT sensitization synergetically regulates the rotary motion of lanthanide‐complexed motors in thermal helix inversion steps.
Polyoxazoline‐Based Nanovaccine Synergizes with Tumor‐Associated Macrophage Targeting and Anti‐PD‐1 Immunotherapy against Solid Tumors
Authors: Matos Ana I. , Peres Carina , Carreira Barbara , Moura Liane I. F. , Acúrcio Rita C. , Vogel Theresa , Wegener Erik , Ribeiro Filipa , Afonso Marta B. , Santos Fábio M. F. , Martínez‐Barriocanal Águeda , Arango Diego , Viana Ana S. , Góis Pedro M. P. , Silva Liana C. , Rodrigues Cecília M. P. , Graca Luis , Jordan Rainer , Satchi‐Fainaro Ronit , Florindo Helena F.
Published: July 2023

Immune checkpoint blockade reaches remarkable clinical responses. However, even in the most favorable cases, half of these patients do not benefit from these therapies in the long term. It is hypothesized that the activation of host immunity by co‐delivering peptide antigens, adjuvants, and regulators of the transforming growth factor (TGF)‐β expression using a polyoxazoline (POx)‐poly(lactic‐co‐glycolic) acid (PLGA) nanovaccine, while modulating the tumor‐associated macrophages (TAM) function within the tumor microenvironment (TME) and blocking the anti‐programmed cell death protein 1 (PD‐1) can constitute an alternative approach for cancer immunotherapy. POx‐Mannose (Man) nanovaccines generate antigen‐specific T‐cell responses that control tumor growth to a higher extent than poly(ethylene glycol) (PEG)‐Man nanovaccines. This anti‐tumor effect induced by the POx‐Man nanovaccines is mediated by a CD8+‐T cell‐dependent mechanism, in contrast to the PEG‐Man nanovaccines. POx‐Man nanovaccine combines with pexidartinib, a modulator of the TAM function, restricts the MC38 tumor growth, and synergizes with PD‐1 blockade, controlling MC38 and CT26 tumor growth and survival. This data is further validated in the highly aggressive and poorly immunogenic B16F10 melanoma mouse model. Therefore, the synergistic anti‐tumor effect induced by the combination of nanovaccines with the inhibition of both TAM‐ and PD‐1‐inducing immunosuppression, holds great potential for improving immunotherapy outcomes in solid cancer patients.
Recyclable Thin‐Film Soft Electronics for Smart Packaging and E‐Skins
Authors: Reis Carneiro Manuel , de Almeida Aníbal T. , Tavakoli Mahmoud , Majidi Carmel
Published: July 2023

Despite advances in soft, sticker‐like electronics, few efforts have dealt with the challenge of electronic waste. Here, this is addressed by introducing an eco‐friendly conductive ink for thin‐film circuitry composed of silver flakes and a water‐based polyurethane dispersion. This ink uniquely combines high electrical conductivity (1.6 × 105S m−1), high resolution digital printability, robust adhesion for microchip integration, mechanical resilience, and recyclability.  Recycling is achieved with an ecologically‐friendly processing method to decompose the circuits into constituent elements and recover the conductive ink with a decrease of only 2.4% in conductivity. Moreover, adding liquid metal enables stretchability of up to 200% strain, although this introduces the need for more complex recycling steps. Finally, on‐skin electrophysiological monitoring biostickers along with a recyclable smart package with integrated sensors for monitoring safe storage of perishable foods are demonstrated.
Field‐Induced Transparent Electrode‐Integrated Transparent Solar Cells and Heater for Active Energy Windows: Broadband Energy Harvester
Authors: Patel Malkeshkumar , Kim Sangho , Kim Joondong
Published: July 2023

Invisible power generation by natural and artificial light enables sustainability by onsite‐power deployment, lower cost, and minimal burden on the built environment. However, dark, opaque photovoltaics limit light utilization in a transparent way. Herein, it is proposed that the active energy window (AEW) invisibly features power production, providing higher freedom for onsite power generators in window objects without limiting human vision. The AEW has a transparent photovoltaic (TPV) for onsite power and a transparent heater (TH) to remove the effects of shadows from snow and recover the power lost. Moreover, a heating function is applied to remove the effects of weathering related to snow. The proposed prototype integrates a TPV‐TH, offering ultraviolet (UV)‐blocking, daylighting, thermal comfort, and onsite power with a power conversion efficiency of 3% (AM1.5G). Field‐induced transparent electrodes are applied to the TPV‐TH and designed considering the AEW. Owing to these electrodes, the AEW ensure a wide field‐of‐view without optical dead zones, ensuring see‐through vision. The first TPV‐TH integration is performed into a 2 cm2‐window that generates onsite power of 6 mW and has an average visible transmittance of ≈39%. It is believed that light can be utilized with comfort through the AEW in self‐sustainable buildings and vehicles.
Measured task load in directed observers versus active participants undergoing high‐fidelity simulation education in a critical care setting
Authors: Devlin‐Hegedus Jessica , Miller Matthew , Cooke Sean , Ware Sandra , Richmond Clare
Published: July 2023

Objectives

The use of directed observers in high‐fidelity simulation education is increasingly common. While evidence suggests similar educational outcomes for directed observers compared to active participants in technical skills, it remains uncertain if this benefit also exists for senior clinicians, especially in mental workload. We sought to compare the workload between active participants and directed observers using an objective measure.

Methods

We performed a prospective, repeated‐measures observational study during the New South Wales Ambulance Aeromedical Operations induction training from 2019 to 2020. Participants included senior critical care doctors, paramedics, and nurses undergoing high‐fidelity simulation of prehospital and interhospital aeromedical missions. Task load was measured using the National Aeronautics and Space Administration task load index (NASA‐TLX) administered following each simulation debrief. Prehospital and interhospital simulations were compared separately by building a multilevel model for complete case and all study data. Post hoc comparisons of NASA‐TLX score for each group were performed using estimated marginal means (EMMs).

Results

We enrolled 70 participants, comprising 49 physicians (70%), 19 paramedics (27%), and two flight nurses (3%). From the complete case analysis, statistically significant differences were observed for total NASA‐TLX scores between active participants and directed observers in both prehospital (participant EMM 78, observer EMM 65, estimated difference −13, 95% confidence interval [CI] −20 to −7) and interhospital simulations (participant EMM 69, observer EMM 59, estimated difference −10, 95% CI −16 to −3). When all available data were included, the pattern of results did not change.

Conclusions

In our sample of senior clinicians, the task load experienced by both active participants and directed observers in high‐fidelity simulation education was high for both prehospital and interhospital simulation exercises. The statistically significant differences we report are unlikely to be practically significant. Our results support the use of directed observers when resource limitations do not allow all course attendees to participate in every simulation.
Efficient CO2 photoreduction enabled by the energy transfer pathway in metal‐organic framework
Authors: Liu Hai‐Xiong , Si Duan‐Hui , Smith Mallory F. , Li Ren‐Fu , Li Xi‐Ya , Li Lan , Huang Hai‐Bo , Fang Zhi‐Bin , Zhou Hong‐Cai , Liu Tian‐Fu
Published: July 2023

Many studies in metal‐organic frameworks (MOFs) aiming for high photocatalytic activity resort to self‐assembling both energy donor and acceptor building units in skeleton to achieve effective energy transfer, which, however, usually needs tedious synthetic procedure and design of a new MOF. In this work, we demonstrated that building a Förster resonance energy transfer (FRET) pathway can be realized through suitable molecular doping in a given MOF structure without altering the original porous structure, presenting an alternative strategy to design efficient photocatalysts for CO2 reduction. In situ electron spin resonance, ultrafast transient absorption spectroscopy, and computational studies reveal that the FRET‐induced excitation has dramatically altered the exciton transfer pathway in structure and facilitated electron‐hole separation. As a result, the molecular doped MOFs synthesized through one‐pot reaction show outstanding selectivity (96%) and activity (1314 μmol·g−1·h−1) for CO production versus almost no activity for the pristine MOFs, and this result stands out from existing competitors. Furthermore, the reaction mechanism was proposed and the intermediate signals were detected by in situ diffuse reflectance infrared Fourier transform spectroscopies. This study presents a clear picture of building FRET process in MOFs through molecular doping and provides a new design strategy for MOF‐based photocatalysts.
Facile Directed Synthesis of (Z)‐1‐(Aryl(arylimino)methyl)piperidine‐2,6‐diones from C,N‐Diarylformamidines
Authors: Trukhanova Yulia A. , Spiridonova Dar'ya V. , Kuvaeva Elena V. , Chernov Nikita M. , Alekseeva Galina M. , Sopova Marina V. , Fedorova Elena V. , Yakovlev Igor P.
Published: July 2023

A simple methodology has been developed for the synthesis of previously unstudied N‐substituted glutarimide derivatives – (Z)‐1‐(aryl(arylimino)methyl)piperidine‐2,6‐diones 4 a–p obtained in one step from C,N‐diarylformamidines 1 a–p and glutaric anhydride 6 with product yields from 46 up to 88 % and chromatographic purity from 94 to 99 %. The structures of the obtained compounds were proved using NMR spectroscopy 1H, 13C, X‐ray diffraction analysis, mass spectroscopy, and elemental analysis. An in vivo study of the analgesic activity of a representative of series 4 a was carried out.
Updated Bounds on Axion‐Like Particle Dark Matter with the Optical MUSE‐Faint Survey
Authors: Todarello Elisa
Published: July 2023

Bounds are derived on the axion‐like particle (ALP) to two‐photon coupling in the mass range 2.65 − 5.27 eV. The bounds are obtained by searching for the signal from ALP decay in the Multi Unit Spectroscopic Explorer (MUSE) observations of five dwarf spheroidal galaxies, under the assumption that ALPs constitute the dark matter component of the haloes. These bounds are of the same order and improve on the robustness of those of Regis et al., (2021), and currently represent the strongest bounds within the considered mass range.
Triazinium Ligation: Bioorthogonal Reaction of N1‐Alkyl 1,2,4‐Triazinium Salts**
Authors: Šlachtová Veronika , Bellová Simona , La‐Venia Agustina , Galeta Juraj , Dračínský Martin , Chalupský Karel , Dvořáková Alexandra , Mertlíková‐Kaiserová Helena , Rukovanský Peter , Dzijak Rastislav , Vrabel Milan
Published: July 2023

The development of reagents that can selectively react in complex biological media is an important challenge. Here we show that N1‐alkylation of 1,2,4‐triazines yields the corresponding triazinium salts, which are three orders of magnitude more reactive in reactions with strained alkynes than the parent 1,2,4‐triazines. This powerful bioorthogonal ligation enables efficient modification of peptides and proteins. The positively charged N1‐alkyl triazinium salts exhibit favorable cell permeability, which makes them superior for intracellular fluorescent labeling applications when compared to analogous 1,2,4,5‐tetrazines. Due to their high reactivity, stability, synthetic accessibility and improved water solubility, the new ionic heterodienes represent a valuable addition to the repertoire of existing modern bioorthogonal reagents.
Practical Synthesis of Dendritic Hyperbranched Polyacrylates and Their Topological Block Polymers by Organotellurium‐Mediated Emulsion Polymerization in Water**
Authors: Jiang Yuhan , Kibune Masato , Tosaka Masatoshi , Yamago Shigeru
Published: July 2023

The practical synthesis of structurally controlled hyperbranched polymers (HBPs) by organotellurium‐mediated radical polymerization (TERP) in water under emulsion conditions is reported. Copolymerization of vinyltelluride named evolmer, which induces controlled branch structure, and acrylates with TERP chain transfer agent (CTA) in water afforded HBPs having dendron structure. The molecular weight, dispersity, branch number, and branch length of the HBPs were controlled by changing the amount of CTA, evolmer, and acrylate monomers. HB‐poly(butyl acrylate)s (HBPBAs) with up to the 8th generation having an average of 255 branches were successfully synthesized. As the monomer conversion reached nearly quantitative and the obtained polymer particles were well dispersed in water, the method is highly suitable for synthesizing topological block polymers, block polymers consisting of different topologies. Thus, linear‐block‐HB, HB‐block‐linear, and HB‐block‐HB‐PBAs with the controlled structure were successfully synthesized by adding the second monomer(s) to the macro‐CTA. The intrinsic viscosity of the resulting homo‐ and topological block PBAs was systematically controlled by the degree of the branch, the branch length, and the topology. Therefore, the method opens the possibility of obtaining various HBPs with diverse branch structures and tuning the polymer properties by the polymer topology.
Triphosphat‐Pronucleotid (TriPPPro)‐Reporter mit Optimierten Zellpermeablen Farbstoffen zum Metabolischen Labeling von Zellulärer und Viraler DNA in Lebenden Zellen
Authors: Sterrenberg Vincente T. , Stalling Dörte , Knaack J. Iven H. , Soh Timothy K. , Bosse Jens B. , Meier Chris
Published: July 2023

Das metabolische Labeling von Nucleinsäuren in lebenden Zellen ist von äußerstem Interesse, um die Dynamik des Nucleinsäure‐Stoffwechsels in Echtzeit zu verfolgen und hat somit das Potenzial, neue Einblicke in die Zellbiologie sowie in Pathogen‐Wirtszell‐Interaktionen zu liefern. Eine katalysatorfreie Diels–Alder‐Reaktion mit inversem Elektronenbedarf (iEDDA) mit Nucleosiden, die eine hochreaktive Gruppe wie das axiale 2‐trans‐Cycloocten (2TCOa) tragen, ist ideal geeignet, um die intrazelluläre Markierung von DNA zu ermöglichen. Da Triphosphate von Nucleosiden nicht membranpermeabel sind, ist, nach der Aufnahme in die Zelle, die Phosphorylierung der modifizierten Nucleoside durch zelluläre Kinasen erforderlich. Leider schränkt dabei das enge Substratfenster der meisten endogenen Kinasen die Verwendung von Nucleosid‐Analoga mit hochreaktiven Gruppen ein. Hier wenden wir unseren TriPPPro‐ (Triphosphat‐Pronucleotid) Ansatz an, um einen hoch reaktiven 2TCOa‐modifizierten 2′‐Desoxycytidintriphosphat‐Reporter direkt in lebenden Zellen freizusetzen. Wir zeigen, dass dieses Nucleosidtriphosphat metabolisch in de novo synthetisierte zelluläre und virale DNA eingebaut wird und mit hochreaktiven und zellpermeablen Fluoreszenzfarbstoff‐Tetrazin‐Konjugaten via iEDDA markiert werden kann, um DNA in lebenden Zellen direkt sichtbar zu machen. Damit stellen wir die erste umfassende Methode zur Visualisierung zellulärer und viraler Nucleinsäuren in lebenden Zellen vor.
Mehrere Triplett‐Metall‐zentrierte Jahn–Teller‐Isomere bestimmen die temperaturabhängigen Lumineszenzlebensdauern in [Ru(bpy)3]2+
Authors: Hernández‐Castillo David , Nau Roland E. P. , Schmid Marie‐Ann , Tschierlei Stefanie , Rau Sven , González Leticia
Published: July 2023

Ein genaues Verständnis der Faktoren, welche die Lumineszenzlebensdauer von Übergangsmetallverbindungen bestimmen, ist für Anwendungen in der Photokatalyse und der photodynamischen Therapie von entscheidender Bedeutung. Die im Falle von [Ru(bpy)3]2+ (bpy=2,2’‐Bipyridin) allgemein akzeptierte Theorie besagt, dass die Emissionslebensdauer durch Optimierung der Energiebarriere zwischen dem emittierenden Triplett‐Zustand des Metall‐Liganden‐Ladungstransfers (3MLCT) und dem thermisch aktivierten Triplett‐Zustand des Metall‐Zentrums (3MC), oder der Energielücke zwischen beiden Zuständen gesteuert werden kann. Hier zeigen wir, dass dies nicht allgemeingültig ist. Darüber hinaus demonstrieren wir, dass die Betrachtung eines einzelnen Relaxationspfades, der vom energetisch niedrigsten Minimum aus bestimmt wird, zu falschen Vorhersagen der temperaturabhängigen Emissionslebensdauer führt. Stattdessen erhalten wir eine ausgezeichnete Übereinstimmung mit den experimentellen temperaturabhängigen Lebensdauern, wenn ein erweitertes kinetisches Modell herangezogen wird, welches alle Pfade im Zusammenhang mit mehreren Jahn–Teller‐Isomeren und ihren effektiven Reaktionsbarrieren beinhaltet. Diese Konzepte sind für das Design weiterer lumineszierender Übergangsmetallkomplexe mit individuell angepassten Emissionslebensdauern auf der Grundlage theoretischer Vorhersagen unerlässlich.
A TriPPPro‐Nucleotide Reporter with Optimized Cell‐Permeable Dyes for Metabolic Labeling of Cellular and Viral DNA in Living Cells
Authors: Sterrenberg Vincente T. , Stalling Dörte , Knaack J. Iven H. , Soh Timothy K. , Bosse Jens B. , Meier Chris
Published: July 2023

The metabolic labeling of nucleic acids in living cells is highly desirable to track the dynamics of nucleic acid metabolism in real‐time and has the potential to provide novel insights into cellular biology as well as pathogen‐host interactions. Catalyst‐free inverse electron demand Diels–Alder reactions (iEDDA) with nucleosides carrying highly reactive moieties such as axial 2‐trans‐cyclooctene (2TCOa) would be an ideal tool to allow intracellular labeling of DNA. However, cellular kinase phosphorylation of the modified nucleosides is needed after cellular uptake as triphosphates are not membrane permeable. Unfortunately, the narrow substrate window of most endogenous kinases limits the use of highly reactive moieties. Here, we apply our TriPPPro (triphosphate pronucleotide) approach to directly deliver a highly reactive 2TCOa‐modified 2′‐deoxycytidine triphosphate reporter into living cells. We show that this nucleoside triphosphate is metabolically incorporated into de novo synthesized cellular and viral DNA and can be labeled with highly reactive and cell‐permeable fluorescent dye‐tetrazine conjugates via iEDDA to visualize DNA in living cells directly. Thus, we present the first comprehensive method for live‐cell imaging of cellular and viral nucleic acids using a two‐step labeling approach.
Synergistic Metal‐Nonmetal Active Sites in a Metal‐Organic Cage for Efficient Photocatalytic Synthesis of Hydrogen Peroxide in Pure Water
Authors: Lu Jia‐Ni , Liu Jing‐Jing , Dong Long‐Zhang , Lin Jiao‐Min , Yu Fei , Liu Jiang , Lan Ya‐Qian
Published: July 2023

Photocatalytic synthesis of hydrogen peroxide (H2O2) is a potential clean method, but the long distance between the oxidation and reduction sites in photocatalysts hinders the rapid transfer of photogenerated charges, limiting the improvement of its performance. Here, a metal‐organic cage photocatalyst, Co14(L−CH3)24, is constructed by directly coordinating metal sites (Co sites) used for the O2 reduction reaction (ORR) with non‐metallic sites (imidazole sites of ligands) used for the H2O oxidation reaction (WOR), which shortens the transport path of photogenerated electrons and holes, and improves the transport efficiency of charges and activity of the photocatalyst. Therefore, it can be used as an efficient photocatalyst with a rate of as high as 146.6 μmol g−1 h−1 for H2O2 production under O2‐saturated pure water without sacrificial agents. Significantly, the combination of photocatalytic experiments and theoretical calculations proves that the functionalized modification of ligands is more conducive to adsorbing key intermediates (*OH for WOR and *HOOH for ORR), resulting in better performance. This work proposed a new catalytic strategy for the first time; i.e., to build a synergistic metal‐nonmetal active site in the crystalline catalyst and use the host–guest chemistry inherent in the metal‐organic cage (MOC)to increase the contact between the substrate and the catalytically active site, and finally achieve efficient photocatalytic H2O2 synthesis.
Gas chromatography—vacuum ultraviolet spectroscopy in petroleum and fuel analysis
Authors: Kaplitz Alexander S. , Schug Kevin A.
Published: July 2023

In the modern world, energy and fuels are of utmost importance. Rapid characterization of petroleum and other hydrocarbon‐based fuel is a well‐researched field. Gas chromatography has traditionally been used to separate the different species and characterize the chemical content in fuels. Ideally, every molecule would be separated and characterized, but due to the complexity of the petroleum matrix, many compounds coelute. With the help of different detectors, more information can be gained, but there does not exist a single detector that can unambiguously differentiate and identify every compound. Vacuum ultraviolet spectroscopy (VUV) is a relatively new detector that can alleviate many limitations of other detectors. Based on spectroscopic absorption, VUV detection can provide qualitative and quantitative information regarding the composition of different fuels. It also provides certain advantages, allowing the deconvolution of coeluting peaks and differentiation between constitutional isomers. VUV has been used to classify the range of chemical components in many diverse fuel samples. Here, the contributions of VUV detection to petrochemical analysis to date are reviewed.
Morphological Transformation of Self‐Assembled Peptide Nanostructures for Bioimaging Applications
Authors: Xu Ying , Jiang Qiaochu , Sun Xianbao , Liang Gaolin
Published: July 2023

Stimuli‐triggered in‐situ morphological transformation of peptide nanomaterials may enhance the on‐site accumulation and retention of the imaging agent cargos in the stimuli‐rich regions, thus enabling precise, sensitive, and prolonged imaging of diseases. Moreover, this strategy permits the co‐delivery of contrast agents and drugs with the smart “turn‐on” ability, allowing for efficient disease theranostics. In light of the significance of this strategy in designing smart biomedical peptide materials, which remains scarcely reviewed in recent years, we herein provide this review. We summarize the bioimaging applications (i. e., fluorescence imaging, magnetic resonance imaging, and photoacoustic imaging) of these smart morphological transformation‐based peptide materials, and highlight the remarkable breakthroughs. Besides, challenges to be addressed in this field are discussed.
A hydrophobic/oleophilic silica‐cellulose composite aerogel for oil–water separation
Authors: Sun Yue , Bai Jiaojiao , Wang Zhe , Li Huabin , Dong Hua
Published: July 2023

A cellulose aerogel with very low overall density is fabricated by freeze‐drying aqueous cellulose solution. A hydrophobic/oleophilic cellulose aerogel is further fabricated by coating the cellulose aerogel with hexyltrimethoxysilane‐modified SiO2 nanoparticles. The features of the developed hydrophobic/oleophilic cellulose aerogel are characterized with density and porosity measurement, infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and contact angle measurement. Finally, the oil absorption performance of the developed hydrophobic/oleophilic cellulose aerogel is investigated. The results show that SiO2 nanoparticles have been successfully loaded on the surface of the aerogel backbone after fulfillment of fabrication, and the surface of the aerogel turns to be hydrophobic/oleophilic (water contact angle 131° and oil contact angle 0°). The oil absorption experiment results show that the absorption capacity for organic solvents is from 10 to 21 times the initial aerogel weight, depending on the density of the absorbed organic solvents. In addition, the aerogel still maintains good stability in high temperature, strong acid or strong base conditions. Furthermore, the aerogel also shows good performance in separating oil from oil–water mixtures. This hydrophobic/oleophilic cellulose aerogel can be a promising choice for remedying water pollution caused by oil contamination.
Identifying potential insecticide resistance markers through genomic‐level comparison of Bemisia tabaci (Gennadius) lines
Authors: Wang Hua‐Ling , Rao Qiong , Chen Zhen‐Zhu
Published: July 2023

The invasive whitefly (Bemisia tabaci) MED is one of the most economically damaging plant pests. The extensive use of insecticide over decades has led to that the invasive B. tabaci MED has developed resistance to a wide range of insecticide classes, but little is known about the genetic background associated with resistance. To this end, we conducted a comparative genome‐wide analysis of single‐base nucleotide polymorphisms between MED whitefly lines collected from fields that were recently infested and an insecticide‐susceptible MED whitefly line collected in 1976. First, low‐coverage genome sequencings were conducted on DNA isolated from individual whiteflies. The sequencing results were evaluated using an available B. tabaci MED genome as a reference. Significant genetic differences were discovered between MED whitefly lines collected from fields that were recently infested and an insecticide‐susceptible MED whitefly line based on the principal component analyses. Top GO categories and KEGG pathways that might be involved in insecticide resistance development were identified, and several of them have not been previously associated with resistance. Additionally, we identified several genetic loci with novel variations including Cytochrome P450 monooxygenases (P450s), UDP‐glucuronosyltransferases (UGTs), Glutathione S‐transferases (GSTs), esterase, carboxyl‐esterases (COE), ABC transporters, fatty acyl‐CoA reductase, voltage‐gated sodium channels, GABA receptor, and cuticle proteins (CPs) that were previously reported to have close associations with pesticide resistance in well‐studied insect groups that provide an essential resource for the design of insecticide resistance–linked loci arrays insecticide. Our results was obtained solely on resequencing genome data sets, more pesticide bio‐assays combined with omics datasets should be further used to verify the markers identified here.