bluuebunny/crossref_metadata_2025_split huggingface dataset:
Surface Oxygen Coordination of Hydrogen Bond Chemistry for Aqueous Ammonium Ion Hybrid Supercapacitor
Authors: Chen Qiang , Li Hang , Lou Xuan , Zhang Jianli , Hou Guangya , Lu Jun , Tang Yiping 
Published: January 2023

AbstractAqueous ammonium ion hybrid supercapacitor (A‐HSC) combines the charge storage mechanisms of surface adsorption and bulk intercalation, making it a low‐cost, safe, and sustainable energy storage candidate. However, its development is hindered by the low capacity and unclear charge storage fundamentals. Here, the strategy of phosphate ion‐assisted surface functionalization is used to increase the ammonium ion storage capacity of an α‐MoO3 electrode. Moreover, the understanding of charge storage mechanisms via structural characterization, electrochemical analysis, and theoretical calculation is advanced. It is shown that NH4+ intercalation into layered α‐MoO3 is not dominant in the A‐HSC system; rather, the charge storage mainly depends on the adsorption energy of surface “O” to NH4+. It is further revealed that the hydrogen bond chemistry of the coordination between “O” of surface phosphate ion and NH4+ is the reason for the capacity increase of MoO3. This study not only advances the basic understanding of rechargeable aqueous A‐HSC but also demonstrates the promising future of surface engineering strategies for energy storage devices.
Nanoscale Hafnium Metal–Organic Frameworks Enhance Radiotherapeutic Effects by Upregulation of Type I Interferon and TLR7 Expression
Authors: Choi Eunseo , Landry Madeleine , Pennock Nathan , Neufeld Megan , Weinfurter Katherine , Goforth Andrea , Walker Joshua , Sun Conroy 
Published: January 2023

AbstractRecent preclinical and clinical studies have highlighted the improved outcomes of combination radiotherapy and immunotherapy. Concurrently, the development of high‐Z metallic nanoparticles as radiation dose enhancers has been explored to widen the therapeutic window of radiotherapy and potentially enhance immune activation. In this study, folate‐modified hafnium‐based metal–organic frameworks (HfMOF‐PEG‐FA) are evaluated in combination with imiquimod, a TLR7 agonist, as a well‐defined interferon regulatory factor (IRF) stimulator for local antitumor immunotherapy. The enhancement of radiation dose deposition by HfMOF‐PEG‐FA and subsequent generation of reactive oxygen species (ROS) deregulates cell proliferation and increases apoptosis. HfMOF‐PEG‐FA loaded with imiquimod (HfMOF‐PEG‐FA@IMQ) increases DNA double‐strand breaks and cell death, including apoptosis, necrosis, and calreticulin exposure, in response to X‐ray irradiation. Treatment with this multipronged therapy promotes IRF stimulation for subsequent interferon production within tumor cells themselves. The novel observation is reported that HfMOF itself increases TLR7 expression, unexpectedly pairing immune agonist and receptor upregulation in a tumor intrinsic manner, and supporting the synergistic effect observed with the γH2AX assay. T‐cell analysis of CT26 tumors following intratumoral administration of HfMOF‐PEG‐FA@IMQ with radiotherapy reveals a promising antitumor response, characterized by an increase in CD8+ and proliferative T cells.
A Ti‐Doped Chemical Vapor Deposition Diamond Device as Artificial Synapse for Neuromorphic Applications
Authors: Battistoni Silvia , Carcione Rocco , Tamburri Emanuela , Erokhin Victor , Terranova Maria Letizia , Iannotta Salvatore 
Published: January 2023

AbstractThe great demand of multifunctional portable electronic products in daily life and the need of a large integration of memories with logic devices and sensors, have increased the interest in the identification of suitable materials for neuromorphic computing applications. Major innovations in this direction have been achieved by exploring materials belonging to different fields of applications and taking advantage of already consolidated deposition methods. Despite the great interest in the field and the large use in complementary applications such as sensing electrodes, neural and cellular interfaces, the use of diamond‐like materials in neuromorphic applications is still limited to a few examples. Herein, the development of a synaptic element based on high‐quality polycrystalline diamond layers containing Ti inclusions showing a marked and reproducible resistance switching behavior is reported. Realized by means of a hybrid chemical vapor deposition‐powder flowing technique, this titanium doped diamond shows a 3D polycrystalline organization that is characterized by globular grains of a few microns. The coupling of Raman spectroscopy, X‐ray photoelectron spectroscopy, and X‐ray diffraction analyses confirms the good quality of diamond phase and convincingly points out the inclusion of the titanium species within the diamond lattice.
Self‐Driven Ni‐Based Electrochromic Devices for Energy‐Efficient Smart Windows
Authors: Zhang He , Feng Jiayun , Sun Fangyuan , Zhou Dongyan , Cao Ge , Wang Shang , Hu Xuanyi , Ma Jingxuan , Su Fengyu , Tian Yanqing , Tian Yanhong 
Published: January 2023

AbstractElectrochromic devices (ECDs) with adjustable transmittance have opened new opportunities to the development of smart windows for energy‐efficiency building. However, the switching between colored and bleached state of conventional ECD will bring extra energy consumption, the design of high‐performance ECD with low consumption is still an elusive goal. To address this issue, a self‐driven and energy‐saving Ni anode‐based ECD using Prussian blue as electrochromic material is developed. During the day, it can be colored by solar energy. By contrast, it can spontaneously bleach when the ECD's anode and cathode are short‐circuiting using the internal redox potential during the night. It is worth noting that no extra energy is inputted in the coloring‐bleaching cycle. In comparison with the ECD using electrolyte with high Ni2+ (K+:Ni2+ = 1:9) or high K+ (K+:Ni2+ = 9:1) concentration with poor optical contrast and cyclic stability (failed <100 cycles), the Ni‐based ECD with the electrolyte containing equal amount of K+ and Ni2+ exhibits a high optical contrast (39.45%), good coloration response time (6 s), and excellent stability (1000 cycles). These properties suggest that the Ni‐based electrochromic configuration is expected to be a catalyst for the development of energy‐storage EC smart window in the future.
Freeform Membranes with Tunable Permeability in Microfluidics
Authors: Hirschwald Lukas T. , Brosch Sebastian , Linz Georg , Linkhorst John , Wessling Matthias 
Published: January 2023

AbstractMicrofluidic systems offer a multitude of advantages over classical techniques in the fields of biomedical and chemical research. Unit operations such as sample pre‐treatment, mixing, reactions, and especially separation and purification operations can be realized on microfluidic platforms enabling rapid prototyping and facile parallelization on the laboratory scale. However, the fabrication and integration of porous membranes in microfluidics poses several problems. Material development, membrane geometry, and membrane integration are three main questions to be addressed in this context. Herein, a durable and versatile method to anchor free‐form membranes with tunable microgeometry to surfaces, enabling the fabrication of stable, multi‐material microfluidic systems for different potential applications is shown. In addition, the influence of the macro‐ and microgeometry that is the shape and porosity of a membrane on key performance indicators such as diffusivity and permeation of tracer molecules is investigated. The presented characterization methods will enable a better understanding of microfluidic modules with incorporated membranes.
Harnessing Soft Elasticity of Liquid Crystal Elastomers to Achieve Low Voltage Driven Actuation
Authors: Annapooranan Raja , Wang Yang , Cai Shengqiang 
Published: January 2023

AbstractDielectric elastomers (DE) are soft electromechanical transducers that can generate large, rapid, and reversible deformation under an electric field. Despite being one of the leading candidates for soft actuators, the widespread applications of dielectric elastomers are restricted by the high voltage requirement (1–10 kV) for thin film DEs, which increases the system complexity and pose a potential safety threat for humans. In this work, a new class of dielectric elastomer actuators using liquid crystal elastomers (DLCEs) is reported. Soft elasticity of DLCEs and the high dielectric constant are utilized to reduce the actuation voltage. Freestanding DLCE thin film actuators (≈20 µm) are fabricated, which can generate large actuation strains (≈88%) at 400 V, an input voltage almost one order of magnitude lower compared to typical dielectric elastomers actuators. This allows to develop a soft tunable bilayer DE lens, which can achieve a 21% focal length variation at 500 V.
Visible‐Light‐Activated Molecular Machines Kill Fungi by Necrosis Following Mitochondrial Dysfunction and Calcium Overload
Authors: Santos Ana L. , Beckham Jacob L. , Liu Dongdong , Li Gang , van Venrooy Alexis , Oliver Antonio , Tegos George P. , Tour James M. 
Published: January 2023

AbstractInvasive fungal infections are a growing public health threat. As fungi become increasingly resistant to existing drugs, new antifungals are urgently needed. Here, it is reported that 405‐nm‐visible‐light‐activated synthetic molecular machines (MMs) eliminate planktonic and biofilm fungal populations more effectively than conventional antifungals without resistance development. Mechanism‐of‐action studies show that MMs bind to fungal mitochondrial phospholipids. Upon visible light activation, rapid unidirectional drilling of MMs at ≈3 million cycles per second (MHz) results in mitochondrial dysfunction, calcium overload, and ultimately necrosis. Besides their direct antifungal effect, MMs synergize with conventional antifungals by impairing the activity of energy‐dependent efflux pumps. Finally, MMs potentiate standard antifungals both in vivo and in an ex vivo porcine model of onychomycosis, reducing the fungal burden associated with infection.
Elongated Riboflavin‐Producing Shewanellaoneidensis in a Hybrid Biofilm Boosts Extracellular Electron Transfer
Authors: Zhao Juntao , Li Feng , Kong Shutian , Chen Tao , Song Hao , Wang Zhiwen 
Published: January 2023

AbstractShewanella oneidensis is able to carry out extracellular electron transfer (EET), although its EET efficiency is largely limited by low flavin concentrations, poor biofilm forming‐ability, and weak biofilm conductivity. After identifying an important role for riboflavin (RF) in EET via in vitro experiments, the synthesis of RF is directed to 837.74 ± 11.42 µm in S. oneidensis. Molecular dynamics simulation reveals RF as a cofactor that binds strongly to the outer membrane cytochrome MtrC, which is correspondingly further overexpressed to enhance EET. Then the cell division inhibitor sulA, which dramatically enhanced the thickness and biomass of biofilm increased by 155% and 77%, respectively, is overexpressed. To reduce reaction overpotential due to biofilm thickness, a spider‐web‐like hybrid biofilm comprising RF, multiwalled carbon nanotubes (MWCNTs), and graphene oxide (GO) with adsorption‐optimized elongated S. oneidensis, achieve a 77.83‐fold increase in power (3736 mW m−2) relative to MR‐1 and dramatically reduce the charge‐transfer resistance and boosted biofilm electroactivity. This work provides an elegant paradigm to boost EET based on a synthetic biology strategy and materials science strategy, opens up further opportunities for other electrogenic bacteria.
Chemical Crossover Accelerates Degradation of Lithium Electrode in High Energy Density Rechargeable Lithium–Oxygen Batteries
Authors: Matsuda Shoichi , Ono Manai , Asahina Hitoshi , Kimura Shin , Mizuki Emiko , Yasukawa Eiki , Yamaguchi Shoji , Kubo Yoshimi , Uosaki Kohei 
Published: January 2023

AbstractLithium‐oxygen batteries (LOBs) are promising next‐generation rechargeable battery candidates due to theoretical energy densities that exceed those of conventional lithium‐ion batteries. Although LOB with high cell level energy density has been demonstrated under lean electrolyte and high areal capacity conditions, their cycle life is still poor, and the cell degradation mechanism remains unclear. In the present study, by use of a three‐electrode electrochemical setup and in situ MS analytical techniques, it is revealed that the reaction efficiency of the negative lithium electrode largely decreases due to chemical crossover from the positive oxygen electrode side, such as H2O and CO2. Based on this mechanistic understanding, a LOB with an ultra‐lightweight flexible ceramic‐based solid‐state separator with 6 µm thickness that effectively protects the lithium electrode against chemical crossover without diminishing the energy density of LOBs is fabricated. Notably, a 400 Wh kg−1class LOB exhibits a stable discharge/charged process for >20 cycles. The strategy demonstrated in this study sheds light on the direction for the practical implementation of LOBs with high energy densities and long cycle lives.
Genetic testing in the evaluation of individuals with clinical diagnosis of atypicalSturge–Webersyndrome
Authors: Yeom SangEun , Cohen Bernard , Weiss Clifford R. , Montano Carolina , Wohler Elizabeth , Sobreira Nara , Hammill Adrienne M. , Comi Anne 
Published: January 2023

AbstractSturge–Weber Syndrome (SWS) is a rare vascular malformation disorder characterized by abnormal blood vessels in the brain, skin, and eye. SWS is most commonly caused by a somatic mosaicGNAQ‐p.Arg183Gln variant. In this series, 12 patients presented for clinical evaluation of SWS but were noted to have atypical features, and therefore germline and/or somatic genetic testing was performed. Atypical features included extensive capillary malformation on the body as well as the face, frontal bossing, macrocephaly, telangiectasia, overgrowth of extremities, absence of neurologic signs and symptoms, and family history of vascular malformations. Five patients had a somaticGNAQorGNA11pathogenic variant, one patient had a somatic mosaic likely‐pathogenic variant inPIK3CA,and another one had a somatic mosaic deletion that disruptedPTPRD. The other five patients had germline variants inRASA1,EPHB4, orKIT. Our findings suggest that patients presenting for SWS evaluation who have atypical clinical characteristics may have pathogenic germline or somatic variants in genes other thanGNAQorGNA11. Broad germline and somatic genetic testing in these patients with atypical findings may have implications for medical care, prognosis, and trial eligibility.
An automatic facial landmarking for children with rare diseases
Authors: Hennocq Quentin , Bongibault Thomas , Bizière Matthieu , Delassus Ombline , Douillet Maxime , Cormier‐Daire Valérie , Amiel Jeanne , Lyonnet Stanislas , Marlin Sandrine , Rio Marlène , Picard Arnaud , Khonsari Roman Hossein , Garcelon Nicolas 
Published: January 2023

AbstractTwo to three thousand syndromes modify facial features: their screening requires the eye of an expert in dysmorphology. A widely used tool in shape characterization is geometric morphometrics based on landmarks, which are precise and reproducible anatomical points. Landmark positioning is user dependent and time consuming. Many automatic landmarking tools are currently available but do not work for children, because they have mainly been trained using photographic databases of healthy adults. Here, we developed a method for building an automatic landmarking pipeline for frontal and lateral facial photographs as well as photographs of external ears. We evaluated the algorithm on patients diagnosed with Treacher Collins (TC) syndrome as it is the most frequent mandibulofacial dysostosis in humans and is clinically recognizable although highly variable in severity. We extracted photographs from the photographic database of the maxillofacial surgery and plastic surgery department of Hôpital Necker–Enfants Malades in Paris, France with the diagnosis of TC syndrome. The control group was built from children admitted for craniofacial trauma or skin lesions. After testing two methods of object detection by bounding boxes, a Haar Cascade‐based tool and a Faster Region‐based Convolutional Neural Network (Faster R‐CNN)‐based tool, we evaluated three different automatic annotation algorithms: the patch‐based active appearance model (AAM), the holistic AAM, and the constrained local model (CLM). The final error corresponding to the distance between the points placed by automatic annotation and those placed by manual annotation was reported. We included, respectively, 1664, 2044, and 1375 manually annotated frontal, profile, and ear photographs. Object recognition was optimized with the Faster R‐CNN‐based detector. The best annotation model was the patch‐based AAM (p < 0.001 for frontal faces, p = 0.082 for profile faces and p < 0.001 for ears). This automatic annotation model resulted in the same classification performance as manually annotated data. Pretraining on public photographs did not improve the performance of the model. We defined a pipeline to create automatic annotation models adapted to faces with congenital anomalies, an essential prerequisite for research in dysmorphology.
Radical‐Bridged Heterometallic Single‐Molecule Magnets Incorporating Four Lanthanoceniums
Authors: Zhang Peng , Luo Qian‐Cheng , Zhu Zhenhua , He Wanrong , Song Nan , Lv Junting , Wang Xuning , Zhai Quan‐Guo , Zheng Yan‐Zhen , Tang Jinkui 
Published: January 2023

AbstractThe syntheses and magnetic properties of organometallic heterometallic compounds [K(THF)6]{CoI[(μ3‐HAN)RE2Cp*4]2} (1‐RE) and [K(Crypt)]2{CoI[(μ3‐HAN)RE2Cp*4]2} (2‐RE) containing hexaazatrinaphthylene radicals (HAN⋅3−) and four rare earth (RE) ions are reported. 1‐RE shows isolable species with ligand‐based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2‐RE via one‐electron chemical reduction. Strong electronic communication in mixed‐valency supports stronger overall ferromagnetic behaviors in 2‐RE than 1‐RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1‐Dy and 2‐Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2‐Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1‐Dy. Ligand‐based mixed‐valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln‐SMMs.
Biodegradability of bio‐based and synthetic hydrogels as sustainable soil amendments: A review
Authors: Adjuik Toby A. , Nokes Sue E. , Montross Michael D. 
Published: January 2023

AbstractSuperabsorbent polymers (SAPs), sometimes known as hydrogels, have been proposed as soil amendments to enhance soil water management. But the performance of SAPs as soil amendments depends on their stability in soil. Bio‐based SAPs have been praised as environmentally sustainable due to their apparent fast biodegradation relative to synthetic SAPs. But the fast biodegradation of bio‐based SAPs may come at a cost to their long‐term performance for repeated absorption and release of water in the soil. The purpose of this review is to (i) concisely summarize the methods and mechanisms involved in the biodegradation of different bio‐based and synthetic SAPs, (ii) critically review studies conducted on the biodegradability of bio‐based and synthetic SAPs when used as soil amendments, and (iii) discuss the implications of the biodegradability of bio‐based and synthetic SAPs on their physical properties and stability in soil and (iv) identify potential research directions. Understanding the biodegradability of synthetic compared to bio‐based SAPs and their advantages and disadvantages as soil amendments is important to researchers and farmers when choosing a specific type of SAPs as an agricultural soil amendment.
Boat and Chair Shaped Hexahalogen Synthons
Authors: Swathi Krishna P. E. , Babu Hruidya C. , Nair Nanditha G. , Hariharan Mahesh 
Published: January 2023

AbstractNon‐covalent halogen bonding interactions are quintessential in crystal engineering for the construction of distinctive supramolecular synthons. Here, we report the first crystalline evidences of unique boat and chair shaped cyclic hexahalogen synthons in the crystal structures of α,α,α′,α′,4‐pentabromo‐o‐xylene (PBX) and α,α,α′,α′,4,5‐hexabromo‐o‐xylene (HBX) respectively. Nature and stability of constituent interactions in the supramolecular synthons are scrutinized with the help of quantum‐chemical calculations. Pendás’ interacting quantum atoms approach confirmed the stability of Br⋅⋅⋅Br interactions leading to boat and chair shaped synthons with major contribution from exchange‐correlation. Although both the molecules are achiral in nature, the packing forces guide PBX to crystallize in the chiral space group P21 with a helix‐like orientation while HBX packs in a centrosymmetric P21/n space group. The extended furcations in the pentabromo derivative construct a molecular framework consisting of macrocycles realized through halogen bonding.
Becken aus Beton in Entwässerungsanlagen nach ZTV‐ING
Authors: Alonso Junghanns Maria Teresa , Breitenbücher Rolf , Günther Michael , Haist Michael , Haus Jörg 
Published: January 2023

AbstractBecken aus Beton im Zuge von Bundesfernstraßen sind in der ZTV‐ING geregelt. Unter Berücksichtigung des aktuellen Stands der Technik und der zwischenzeitlich vorliegenden Erfahrungen der Straßenbauverwaltungen sowohl hinsichtlich des Baus als auch des Betriebs von Becken und Pumpenhäusern sollte die Zuordnung dieser Bauteile zu Expositionsklassen überdacht werden. Im vorliegenden Beitrag werden die bei Becken aus Beton relevanten Umwelteinwirkungen differenziert betrachtet und die Hintergründe für eine mögliche Anpassung der bisherigen Festlegungen erläutert. Bei einer globalen Kategorisierung sind nach den heutigen Regelungen viele Bauteile solcher Becken formal der Expositionsklasse XF4 zuzuordnen, woraus sich dann unmittelbar die zwingende Verwendung von LP‐Beton ableitet. Differenzierte Betrachtungen, unter Einbeziehung spezifischer Randbedingungen und langjähriger Erfahrungen, lassen aber auch die Verwendung von Betonen ohne künstlich eingeführte Luftporen zu.
In situ biological particle analyzer based on digital inline holography
Authors: Sanborn Delaney , He Ruichen , Feng Lei , Hong Jiarong 
Published: January 2023

AbstractObtaining in situ measurements of biological microparticles is crucial for both scientific research and numerous industrial applications (e.g., early detection of harmful algal blooms, monitoring yeast during fermentation). However, existing methods are limited to offer timely diagnostics of these particles with sufficient accuracy and information. Here, we introduce a novel method for real‐time, in situ analysis using machine learning (ML)‐assisted digital inline holography (DIH). Our ML model uses a customized YOLOv5 architecture specialized for the detection and classification of small biological particles. We demonstrate the effectiveness of our method in the analysis of 10 plankton species with equivalent high accuracy and significantly reduced processing time compared to previous methods. We also applied our method to differentiate yeast cells under four metabolic states and from two strains. Our results show that the proposed method can accurately detect and differentiate cellular and subcellular features related to metabolic states and strains. This study demonstrates the potential of ML‐driven DIH approach as a sensitive and versatile diagnostic tool for real‐time, in situ analysis of both biotic and abiotic particles. This method can be readily deployed in a distributive manner for scientific research and manufacturing on an industrial scale.