bluuebunny/crossref_metadata_2025_split huggingface dataset:
Harnessing Selectivity and Sensitivity in Ion Sensing via Supramolecular Recognition: A 3D Hybrid Gold Nanoparticle Network Chemiresistor
Authors: Montes‐García Verónica , de Oliveira Rafael Furlan , Wang Ye , Berezin Andrey , Fanjul‐Bolado Pablo , González García María Begoña , Hermans Thomas M. , Bonifazi Davide , Casalini Stefano , Samorì Paolo 
Published: November 2020

AbstractThe monitoring of K+ in saliva, blood, urine, or sweat represents a future powerful alternative diagnostic tool to prevent various diseases. However, several K+ sensors are unable to meet the requirements for the development of point‐of‐care (POC) sensors. To tackle this grand‐challenge, the fabrication of chemiresistors (CRs) based on 3D networks of Au nanoparticles covalently bridged by ad‐hoc supramolecular receptors for K+, namely dithiomethylene dibenzo‐18‐crown‐6 ether is reported here. A multi‐technique characterization allows optimizing a new protocol for fabricating high‐performing CRs for real‐time monitoring of K+ in complex aqueous environments. The sensor shows exceptional figures of merit: i) linear sensitivity in the 10–3 to 10–6 m concentration range; ii) high selectivity to K+ in presence of interfering cations (Na+, Ca2+, and Mg2+); iii) high shelf‐life stability (>45 days); iv) reversibility of K+ binding and release; v) successful device integration into microfluidic systems for real‐time monitoring; vi) fast response and recovery times (<18 s), and v) K+ detection in artificial saliva. All these characteristics make the supramolecular CRs a potential tool for future applications as POC devices, especially for health monitoring where the determination of K+ in saliva is pivotal for the early diagnosis of diseases.
Inverse Opal Films for Medical Sensing: Application in Diagnosis of Neonatal Jaundice
Authors: Nicolas Natalie J. , Duffy Meredith A. , Hansen Anne , Aizenberg Joanna 
Published: November 2020

AbstractA non‐invasive, at‐home test for neonatal jaundice can facilitate early jaundice detection in infants, improving clinical outcomes for neonates with severe jaundice and helping to prevent the development of kernicterus, a type of brain damage whose symptoms include hearing loss, impairment of cognitive capacity, and death. Here a photonic sensor that utilizes color changes induced by analyte infiltration into a chemically functionalized inverse opal structure is developed. The sensor is calibrated to detect differences in urinary surface tension due to increased bile salt concentration in urine, which is symptomatic of abnormal liver function and linked to jaundice. The correlation between neonatal urinary surface tension and excess serum bilirubin, the physiologic cause of neonatal jaundice, is explored. It is shown that these non‐invasive sensors can improve the preliminary diagnosis of neonatal jaundice, reducing the number of invasive blood tests and hospital visits necessary for healthy infants while ensuring that jaundiced infants are treated in a timely manner. The use of inverse opal sensors to measure bulk property changes in bodily fluids can be extended to the detection of several other conditions, making this technology a versatile platform for convenient point‐of‐care diagnosis.
DNA‐Based Nanocarriers to Enhance the Optoacoustic Contrast of Tumors In Vivo
Authors: Joseph James , Baumann Kevin N. , Postigo Alejandro , Bollepalli Laura , Bohndiek Sarah E. , Hernández‐Ainsa Silvia 
Published: November 2020

AbstractOptoacoustic tomography (OT) enables non‐invasive deep tissue imaging of optical contrast at high spatio‐temporal resolution. The applications of OT in cancer imaging often rely on the use of molecular imaging contrast agents based on near‐infrared (NIR) dyes to enhance contrast at the tumor site. While these agents afford excellent biocompatibility and minimal toxicity, they present limited optoacoustic signal generation capability and rapid renal clearance, which can impede their tumor imaging efficacy. In this work, a synthetic strategy to overcome these limitations utilizing biodegradable DNA‐based nanocarrier (DNA‐NC) platforms is introduced. DNA‐NCs enable the incorporation of NIR dyes (in this case, IRDye 800CW) at precise positions to enable fluorescence quenching and maximize optoacoustic signal generation. Furthermore, these DNA‐NCs show a prolonged blood circulation compared to the native fluorophores, facilitating tumor accumulation by the enhanced permeability and retention (EPR) effect. In vivo imaging of tumor xenografts in mice following intravenous administration of DNA‐NCs reveals enhanced OT signals at 24 h when compared to free fluorophores, indicating promise for this method to enhance the optoacoustic signal generation capability and tumor uptake of clinically relevant NIR dyes.
Recent Advances in Growth of Large‐Sized 2D Single Crystals on Cu Substrates
Authors: Fan Yixuan , Li Lin , Yu Gui , Geng Dechao , Zhang Xiaotao , Hu Wenping 
Published: November 2020

AbstractLarge‐scale and high‐quality 2D materials have been an emerging and promising choice for use in modern chemistry and physics owing to their fascinating property profile. The past few years have witnessed inspiringly progressing development in controlled fabrication of large‐sized and single‐crystal 2D materials. Among those production methods, chemical vapor deposition (CVD) has drawn the most attention because of its fine control over size and quality of 2D materials by modulating the growth conditions. Meanwhile, Cu has been widely accepted as the most popular catalyst due to its significant merit in growing monolayer 2D materials in the CVD process. Herein, very recent advances in preparing large‐sized 2D single crystals on Cu substrates by CVD are presented. First, the unique features of Cu will be given in terms of ultralow precursor solubility and feasible surface engineering. Then, scaled growth of graphene and hexagonal boron nitride (h‐BN) crystals on Cu substrates is demonstrated, wherein different kinds of Cu surfaces have been employed. Furthermore, the growth mechanism for the growth of 2D single crystals is exhibited, offering a guideline to elucidate the in‐depth growth dynamics and kinetics. Finally, relevant issues for industrial‐scale mass production of 2D single crystals are discussed and a promising future is expected.
Thiophene‐Bridged Donor–Acceptor sp2‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction
Authors: Xu Shunqi , Sun Hanjun , Addicoat Matthew , Biswal Bishnu P. , He Fan , Park SangWook , Paasch Silvia , Zhang Tao , Sheng Wenbo , Brunner Eike , Hou Yang , Richter Marcus , Feng Xinliang 
Published: November 2020

AbstractPhotoelectrochemical (PEC) water reduction, converting solar energy into environmentally friendly hydrogen fuel, requires delicate design and synthesis of semiconductors with appropriate bandgaps, suitable energy levels of the frontier orbitals, and high intrinsic charge mobility. In this work, the synthesis of a novel bithiophene‐bridged donor–acceptor‐based 2D sp2‐carbon‐linked conjugated polymer (2D CCP) is demonstrated. The Knoevenagel polymerization between the electron‐accepting building block 2,3,8,9,14,15‐hexa(4‐formylphenyl) diquinoxalino[2,3‐a:2′,3′‐c]phenazine (HATN‐6CHO) and the first electron‐donating linker 2,2′‐([2,2′‐bithiophene]‐5,5′‐diyl)diacetonitrile (ThDAN) provides the 2D CCP‐HATNThDAN (2D CCP‐Th). Compared with the corresponding biphenyl‐bridged 2D CCP‐HATN‐BDAN (2D CCP‐BD), the bithiophene‐based 2D CCP‐Th exhibits a wide light‐harvesting range (up to 674 nm), a optical energy gap (2.04 eV), and highest energy occupied molecular orbital–lowest unoccupied molecular orbital distributions for facilitated charge transfer, which make 2D CCP‐Th a promising candidate for PEC water reduction. As a result, 2D CCP‐Th presents a superb H2‐evolution photocurrent density up to ≈7.9 µA cm−2 at 0 V versus reversible hydrogen electrode, which is superior to the reported 2D covalent organic frameworks and most carbon nitride materials (0.09–6.0 µA cm−2). Density functional theory calculations identify the thiophene units and cyano substituents at the vinylene linkage as active sites for the evolution of H2.
Copper Oxide Buffer Layers by Pulsed‐Chemical Vapor Deposition for Semitransparent Perovskite Solar Cells
Authors: Eom Taeyong , Kim Songhee , Agbenyeke Raphael E. , Jung Hyunmin , Shin Seon Min , Lee Young Kuk , Kim Chang Gyoun , Chung Taek‐Mo , Jeon Nam Joong , Park Helen Hejin , Seo Jangwon 
Published: November 2020

AbstractIn semitransparent perovskite solar cells with n–i–p configuration, thermal evaporation is the common method to deposit the sputter buffer material, such as molybdenum oxide and tungsten oxide. Buffer layers are especially necessary when using organic hole transporting layers, as they are more susceptible to get damaged when sputtering the top transparent conducting oxide. However, there is a limited selection of possible materials and limited control of the materials properties by thermal evaporation, which leads to inefficient protection against sputtering and poor air stability. While there have been well‐established buffer layers by atomic layer deposition, including tin oxide, for p–i–n structured semitransparent perovskite solar cells, this is not the case for n–i–p structured devices. Here, copper oxide is demonstrated by pulsed‐chemical vapor deposition incorporated into perovskite solar cells for the sputter buffer layer, which result in stable encapsulated semitransparent devices maintaining over 95% of the maximum efficiency under AM 1.5 G at maximum power point tracking for 150 h without any temperature control.
A Low‐Temperature Additive‐Involved Leaching Method for Highly Efficient Inorganic Perovskite Solar Cells
Authors: Sun Xiuhong , Shao Zhipeng , Rao Yi , Meng Hongguang , Gao Caiyun , Chen Chen , Liu Dachang , Lv Peiliang , Li Zhipeng , Wang Xiao , Cui Guanglei , Pang Shuping 
Published: November 2020

AbstractInorganic CsPbI3 perovskite with an optical bandgap ranging from 1.67 to 1.75 eV is a promising light‐harvesting material as a top cell in tandem solar cells, but its high fabrication temperature can damage the middle layers or the bottom subcells. Here, an additive‐involved leaching method to fabricate CsPbI3 perovskite films is demonstrated, which can decrease the preparation temperature to 100 °C. The CsPbI3 perovskite films with high crystallinity are achieved by a solution assisted reaction between DMAPbI3 and Cs4PbI6 with the leaching of DMA+, Cs+, and I−. The as‐prepared CsPbI3 perovskite films exhibit much superior stability compared to their high‐temperature counterparts. As a result, a power conversion efficiency of over 16% is obtained, and the unencapsulated device maintains over 93% of the initial efficiency after aging for 30 days in air with a relative humidity of 10%.
Biocultural evidence of precise manual activities in an Early Holocene individual of the high‐altitude Peruvian Andes
Authors: Karakostis Fotios Alexandros , Reyes‐Centeno Hugo , Franken Michael , Hotz Gerhard , Rademaker Kurt , Harvati Katerina 
Published: November 2020

AbstractObjectivesCuncaicha, a rockshelter site in the southern Peruvian Andes, has yielded archaeological evidence for human occupation at high elevation (4,480 masl) during the Terminal Pleistocene (12,500–11,200 cal BP), Early Holocene (9,500–9,000 cal BP), and later periods. One of the excavated human burials (Feature 15‐06), corresponding to a middle‐aged female dated to ~8,500 cal BP, exhibits skeletal osteoarthritic lesions previously proposed to reflect habitual loading and specialized crafting labor. Three small tools found in association with this burial are hypothesized to be associated with precise manual dexterity.Materials and methodsHere, we tested this functional hypothesis through the application of a novel multivariate methodology for the three‐dimensional analysis of muscle attachment surfaces (entheses). This original approach has been recently validated on both lifelong‐documented anthropological samples as well as experimental studies in nonhuman laboratory samples. Additionally, we analyzed the three‐dimensional entheseal shape and resulting moment arms for muscleopponens pollicis.ResultsResults show that Cuncaicha individual 15‐06 shows a distinctive entheseal pattern associated with habitual precision grasping via thumb‐index finger coordination, which is shared exclusively with documented long‐term precision workers from recent historical collections. The separate geometric morphometric analysis revealed that the individual'sopponens pollicisenthesis presents a highly projecting morphology, which was found to strongly correlate with long joint moment arms (a fundamental component of force‐producing capacity), closely resembling the form of Paleolithic hunter‐gatherers from diverse geo‐chronological contexts of Eurasia and North Africa.DiscussionOverall, our findings provide the first biocultural evidence to confirm that the lifestyle of some of the earliest Andean inhabitants relied on habitual and forceful precision grasping tasks.
Chirale molekulare Propeller basierend auf Triarylboran‐Ammoniak‐Addukten
Authors: Kemper Michael , Engelage Elric , Merten Christian 
Published: November 2020

AbstractChirale molekulare Propellerkonformationen wurden bereits in verschiedenen Triarylstrukturen, einschließlich Tritylderivaten und Triarylboranen, induziert. Für Boran‐Amin‐Addukte wurde über eine solche induzierte Propellerchiralität bisher noch nicht berichtet, da die Racemisierungsbarrieren in typischen Triarylboranen wie B(C6H5)3 oder B(C6F5)3 zu niedrig sind. Hier wird gezeigt, dass Punktchiralität in den Seitenketten chiraler Triarylboran‐Ammoniak‐Addukte, die zusätzlich zur dativen N→B‐Bindung intramolekulare Wasserstoffbrücken aufweisen, effizient in eine Triarylboran‐Propellerchiralität übertragen werden kann. Unter Verwendung von Röntgenkristallographie und ECD/VCD‐Spektroskopie werden drei Beispiele mit unterschiedlichem sterischem Anspruch der chiralen Alkoxy‐Seitengruppen untersucht. Neben der Aufklärung der Konformationspräferenzen der molekularen Propeller wird gezeigt, dass rechnerisch vorhergesagte Konformationspräferenzen, die für die isolierten, nur implizit solvatisierten Moleküle erhalten wurden, den experimentell beobachteten entgegengesetzt sind.
Eccentric Resistance Training Ameliorates Muscle Weakness in a Mouse Model of Idiopathic Inflammatory Myopathies
Authors: Himori Koichi , Ashida Yuki , Tatebayashi Daisuke , Abe Masami , Saito Yuki , Chikenji Takako , Westerblad Håkan , Andersson Daniel C. , Yamada Takashi 
Published: November 2020

ObjectiveHigh‐force eccentric contractions (ECCs) have traditionally been excluded from rehabilitation programs that include patients with idiopathic inflammatory myopathies (IIMs) due to unverified fear of causing muscle damage and inflammation. In an IIM animal model that used mice with experimental autoimmune myositis (EAM), we undertook this study to investigate whether ECC training can safely and effectively be used to counteract muscle weakness in IIM.MethodsEAM was induced in BALB/c mice by immunization with 3 injections of myosin emulsified in Freund’s complete adjuvant. Controls (n = 12) and mice with EAM (n = 12) were exposed to either an acute bout of 100 ECCs or 4 weeks of ECC training (20 ECCs every other day). To induce ECCs, plantar flexor muscles were electrically stimulated while the ankle was forcibly dorsiflexed.ResultsLess cell damage, as assessed by Evans blue dye uptake, was observed in the muscles of mice with EAM, compared to controls, after an acute bout of 100 ECCs (P < 0.05). Maximum Ca2+‐activated force was decreased in skinned gastrocnemius muscle fibers from mice with EAM, and this was accompanied by increased expression of endoplasmic reticulum (ER) stress proteins, including Gsp78 and Gsp94 (P < 0.05). ECC training prevented the decrease in force and the increase in ER stress proteins and also enhanced the expression and myofibrillar binding of small heat‐shock proteins (HSPs) (P < 0.05), which can stabilize myofibrillar structure and function.ConclusionECC training protected against the reduction in myofibrillar force–generating capacity in an IIM mouse model, and this occurred via inhibition of ER stress responses and small HSP–mediated myofibrillar stabilization.
Normalising the “ugly” to reduce food waste: Exploring the socialisations that form appearance preferences for fresh fruits and vegetables
Authors: Makhal Annesha , Robertson Kirsten , Thyne Maree , Mirosa Miranda 
Published: November 2020

AbstractFruits and vegetables that fail to conform to an aesthetic standard are labelled suboptimal and are often devalued and ultimately discarded. Although consumers perceive suboptimal produce negatively, little is known about how these perceptions are formed and indeed the socialisation process behind them. Using 11 focus group discussions with New Zealand children aged 5–11 years (N = 97), this study explores these socialisations. The results show that family practises around growing and repurposing suboptimal produce, learning about suboptimal produce waste, and acting on that knowledge when making produce choices, facilitates the acceptance of suboptimal produce. Alternatively, observations of parents' produce choice behaviours, and parents' instructions or norms for choosing, preparing, and eating produce socialise the rejection of suboptimal produce. The implications of the study show how environmental sustainability with respect to the food waste problem could be effectively addressed if public policy moves towards strategies that “normalise” suboptimal produce. The interventions recommended show how public campaigns would be more effective by targeting children, who are not only concerned about environmental sustainability, but also through their growing agency and positive pester‐power may influence households to reconsider how food is valued.
Base‐Free Pd‐Catalyzed C−Cl Borylation of Fluorinated Aryl Chlorides
Authors: Budiman Yudha P. , Lorenzen Sabine , Liu Zhiqiang , Radius Udo , Marder Todd B. 
Published: November 2020

AbstractCatalytic C−X borylation of aryl halides containing two ortho‐fluorines has been found to be challenging, as most previous methods require stoichiometric amounts of base and the polyfluorinated aryl boronates suffer from protodeboronation, which is accelerated by ortho‐fluorine substituents. Herein, we report that a combination of Pd(dba)2 (dba=dibenzylideneacetone) with SPhos (2‐dicyclohexylphosphino‐2’,6’‐dimethoxybiphenyl) as a ligand is efficient to catalyze the C‐Cl borylation of aryl chlorides containing two ortho‐fluorine substituents. This method, conducted under base‐free conditions, is compatible with the resulting di‐ortho‐fluorinated aryl boronate products which are sensitive to base.
Unsupported Mg–Alkene Bonding
Authors: Thum Katharina , Friedrich Alexander , Pahl Jürgen , Elsen Holger , Langer Jens , Harder Sjoerd 
Published: November 2020

AbstractThe first intermolecular early main group metal–alkene complexes were isolated. This was enabled by using highly Lewis acidic Mg centers in the Lewis base‐free cations (MeBDI)Mg+ and (tBuBDI)Mg+ with B(C6F5)4− counterions (MeBDI=CH[C(CH3)N(DIPP)]2, tBuBDI=CH[C(tBu)N(DIPP)]2, DIPP=2,6‐diisopropylphenyl). Coordination complexes with various mono‐ and bis‐alkene ligands, typically used in transition metal chemistry, were structurally characterized for 1,3‐divinyltetramethyldisiloxane, 1,5‐cyclooctadiene, cyclooctene, 1,3,5‐cycloheptatriene, 2,3‐dimethylbuta‐1,3‐diene, and 2‐ethyl‐1‐butene. In all cases, asymmetric Mg–alkene bonding with a short and a long Mg−C bond is observed. This asymmetry is most extreme for Mg–(H2C=CEt2) bonding. In bromobenzene solution, the Mg–alkene complexes are either dissociated or in a dissociation equilibrium. A DFT study and AIM analysis showed that the C=C bonds hardly change on coordination and there is very little alkene→Mg electron transfer. The Mg–alkene bonds are mainly electrostatic and should be described as Mg2+ ion‐induced dipole interactions.
Effect of regioregularity and role of heteroatom on the chiral behavior of oligo(heteroalkyl thiophene)s
Authors: Marinelli Martina , Angiolini Luigi , Lanzi Massimiliano , Di Maria Francesca , Salatelli Elisabetta 
Published: November 2020

AbstractNovel optically active oligothiophenes bearing electron‐donating chiral side chains have been prepared by synthetic methods suitable to achieve regioregular head‐to‐tail and head‐to‐head/tail‐to‐tail derivatives. In particular, the chiral (S)‐(2‐methyl)butyl moiety was linked at position 3 of the thiophene ring through heteroatoms, such as S or O, to evaluate its effect on the macro molecular aggregation and, consequently, on the chiroptical properties of the material in the solid state. The materials have been fully characterized and investigated by optical and chiroptical methods upon aggregation both from the solution and as cast films. Compared with the related head‐to‐tail and head‐to‐head/tail‐to‐tail poly(3‐alkyl)thiophene derivatives, with the same optically active moiety directly linked to the ring and possessing a higher polymerization degree, the chiroptical properties of the newly synthesized oligomers were significant, or even better, and provided insight into the role of intrachain–interchain interactions between the heteroatom and the thienyl sulfur atom.
Reversible Hyperpolarization of Ketoisocaproate Using Sulfoxide‐containing Polarization Transfer Catalysts
Authors: Tickner Ben. J. , Ahwal Fadi , Whitwood Adrian C. , Duckett Simon B. 
Published: November 2020

AbstractThe substrate scope of sulfoxide‐containing magnetisation transfer catalysts is extended to hyperpolarize α‐ketoisocaproate and α‐ketoisocaproate‐1‐[13C]. This is achieved by forming [Ir(H)2(κ2‐ketoisocaproate)(N‐heterocyclic carbene)(sulfoxide)] which transfers latent magnetism from p‐H2 via the signal amplification by reversible exchange (SABRE) process. The effect of polarization transfer field on the formation of enhanced 13C magnetization is evaluated. Consequently, performing SABRE in a 0.5 μT field enabled most efficient magnetisation transfer. 13C NMR signals for α‐ketoisocaproate‐1‐[13C] in methanol‐d4 are up to 985‐fold more intense than their traditional Boltzmann derived signal intensity (0.8 % 13C polarisation). Single crystal X‐ray diffraction reveals the formation of the novel catalyst decomposition products [Ir(μ‐H)(H)2(IMes)(SO(Ph)(Me)2)]2 and [(Ir(H)2(IMes)(SO(Me)2))2(μ‐S)] when the sulfoxides methylphenylsulfoxide and dimethylsulfoxide are used respectively.
Instrumentiertes Feuchtemonitoring von historischen Bauwerken mittels elektrischer Impedanzspektroskopie
Authors: Krüger Markus , Lehmann Frank 
Published: November 2020

AbstractIm Rahmen mehrerer Forschungsprojekte zum Erhalt historischer Bauwerke wurde ein drahtloses Monitoringsystem für die kontinuierliche Bauwerksüberwachung entwickelt. Das System erlaubt die Verwendung einer Vielzahl von verschiedenen Sensoren sowohl zur Erfassung der Einwirkungen bzw. Umweltbedingungen, denen die historischen Objekte ausgesetzt sind, als auch der Bauwerksreaktion bzw. der Veränderungen am Bauwerk. Feuchtebedingte Schäden spielen dabei eine bedeutende Rolle und verursachen sehr hohe Kosten. Im vorliegenden Beitrag werden die Grundlagen zur instrumentierten Dauerüberwachung mittels drahtloser Sensornetze zur präventiven Konservierung vorgestellt und die Besonderheiten diskutiert, die auch bei der Weiterentwicklung von Monitoringsystemen berücksichtigt werden können. Die elektrische Impedanzspektroskopie bzw. Impedanzmessungen stellen dabei eine kostengünstige Möglichkeit zur qualitativen Feuchtemessung dar.