bluuebunny/crossref_metadata_2025_split huggingface dataset:
Origin of Ferroelectric Phase Stabilization via the Clamping Effect in Ferroelectric Hafnium Zirconium Oxide Thin Films
Authors: Fields Shelby S. , Cai Truong , Jaszewski Samantha T. , Salanova Alejandro , Mimura Takanori , Heinrich Helge H. , Henry Michael David , Kelley Kyle P. , Sheldon Brian W. , Ihlefeld Jon F. 
Published: August 2022

AbstractThe presence of the top electrode on hafnium oxide‐based thin films during processing has been shown to drive an increase in the amount of metastable ferroelectric orthorhombic phase and polarization performance. This “Clamping Effect,” also referred to as the Capping or Confinement Effect, is attributed to the mechanical stress and confinement from the top electrode layer. However, other contributions to orthorhombic phase stabilization have been experimentally reported, which may also be affected by the presence of a top electrode. In this study, it is shown that the presence of the top electrode during thermal processing results in larger tensile biaxial stress magnitudes and concomitant increases in ferroelectric phase fraction and polarization response, whereas film chemistry, microstructure, and crystallization temperature are not affected. Through etching experiments and measurement of stress evolution for each processing step, it is shown that the top electrode locally inhibits out‐of‐plane expansion in the HZO during crystallization, which prevents equilibrium monoclinic phase formation and stabilizes the orthorhombic phase. This study provides a mechanistic understanding of the clamping effect and orthorhombic phase formation in ferroelectric hafnium oxide‐based thin films, which informs the future design of these materials to maximize ferroelectric phase purity and corresponding polarization behavior.
Unexplained regression in Down syndrome: Management of 51 patients in an international patient database
Authors: Santoro Stephanie L. , Baumer Nicole T. , Cornacchia Michelle , Franklin Catherine , Hart Sarah J. , Haugen Kelsey , Hojlo Margaret A. , Horick Nora , Kishnani Priya S. , Krell Kavita , McCormick Andrew , Milliken Anna L. , Oreskovic Nicolas M. , Pawlowski Katherine G. , Sargado Sabrina , Torres Amy , Valentini Diletta , Vellody Kishore , Skotko Brian G. 
Published: August 2022

AbstractResearch to guide clinicians in the management of the devastating regression which can affect adolescents and young adults with Down syndrome is limited. A multi‐site, international, longitudinal cohort of individuals with a clinical diagnosis of Unexplained Regression in Down syndrome (URDS) was collated through seven Down syndrome clinics. Tiered medical evaluation, a 28‐item core symptom list, and interim management are described naturalistically. Improvement—defined by the percentage of baseline function on a Parent‐reported Functional Score, overall improvement in symptoms on a Clinician‐administered Functional Assessment, or report of management type being associated with improvement—was analyzed. Improvement rates using ECT, IVIG, and others were compared. Across seven clinics, 51 patients with URDS had regression at age 17.6 years, on average, and showed an average 14.1 out of 28 symptoms. Longitudinal improvement in function was achieved in many patients and the medical management, types of treatment, and their impact on function are described. Management with intravenous immunoglobulin (IVIG) was significantly associated with higher rate of improvement in symptoms at the next visit (p = 0.001). Our longitudinal data demonstrates that URDS is treatable, with various forms of clinical management and has a variable course. The data suggests that IVIG may be an effective treatment in some individuals. Our description of the management approaches used in this cohort lays the groundwork for future research, such as development of standardized objective outcome measure and creation of a clinical practice guideline for URDS.
Atomic‐Scale View of Protein‐PEG Interactions that Redirect the Thermal Unfolding Pathway of PEGylated Human Galectin‐3
Authors: Pritzlaff Amanda , Ferré Guillaume , Mulry Emma , Lin Ling , Gopal Pour Niloofar , Savin Daniel A. , Harris Michael E. , Eddy Matthew T. 
Published: August 2022

AbstractPEGylation is a promising approach to address the central challenge of applying biologics, i.e., lack of protein stability in the demanding environment of the human body. Wider application is hindered by lack of atomic level understanding of protein‐PEG interactions, preventing design of conjugates with predicted properties. We deployed an integrative structural and biophysical approach to address this critical challenge with the PEGylated carbohydrate recognition domain of human galectin‐3 (Gal3C), a lectin essential for cell adhesion and potential biologic. PEGylation dramatically increased Gal3C thermal stability, forming a stable intermediate and redirecting its unfolding pathway. Structural details revealed by NMR pointed to a potential role of PEG localization facilitated by charged residues. Replacing these residues subtly altered the protein‐PEG interface and thermal unfolding behavior, providing insight into rationally designing conjugates while preserving PEGylation benefits.
Perovskite Photocatalytic CO2 Reduction or Photoredox Organic Transformation?
Authors: San Martin Jovan , Dang Nhu , Raulerson Emily , Beard Matthew C. , Hartenberger Joseph , Yan Yong 
Published: August 2022

AbstractMetal‐halide perovskites have been explored as photocatalysts for CO2 reduction. We report that perovskite photocatalytic CO2 reduction in organic solvents is likely problematic. Instead, the detected products (i.e., CO) likely result from a photoredox organic transformation involving the solvent. Our observations have been validated using isotopic labeling experiments, band energy analysis, and new control experiments. We designed a typical perovskite photocatalytic setup in organic solvents that led to CO production of up to ≈1000 μmol g−1 h−1. CO2 reduction in organic solvents must be studied with extra care because photoredox organic transformations can produce orders of magnitude higher rate of CO or CH4 than is typical for CO2 reduction routes. Though CO2 reduction is not likely to occur, in situ CO generation is extremely fast. Hence a suitable system can be established for challenging organic reactions that use CO as a feedstock but exploit the solvent as a CO surrogate.
Sunk‐Cost Bias and Knowing When to Terminate a Research Project
Authors: Perignat Elaine , Fleming Fraser F. 
Published: August 2022

AbstractScientific research is an open‐ended quest where success usually triumphs over failure. The tremendous success of science obscures the tendency for the non‐linear discovery process to take longer and cost more than expected. Perseverance through detours and past setbacks requires a significant commitment that is fueled by scientific optimism; the same optimism required to overcome challenges simultaneously exacerbates the very human tendency to continue a line of inquiry when the likelihood of success is minimal, the so‐called sunk‐cost bias. This Viewpoint Article shows how the psychological phenomenon of sunk‐cost bias influences medicinal, pharmaceutical, and organic chemists by comparing how the respective industrial and academic practitioners approach sunk‐cost bias; a series of interviews and illustrative quotes provide a rich trove of data to address this seldom discussed, yet potentially avoidable research cost. The concluding strategies recommended for mitigating against sunk‐cost bias should benefit not only medicinal, pharmaceutical, and organic chemists but a wide array of chemistry practitioners.
A Chemically Recyclable Crosslinked Polymer Network Enabled by Orthogonal Dynamic Covalent Chemistry
Authors: Deng Yuanxin , Zhang Qi , Qu Da‐Hui , Tian He , Feringa Ben L. 
Published: August 2022

AbstractChemical recycling of synthetic polymers offers a solution for developing sustainable plastics and materials. Here we show that two types of dynamic covalent chemistry can be orthogonalized in a solvent‐free polymer network and thus enable a chemically recyclable crosslinked material. Using a simple acylhydrazine‐based 1,2‐dithiolane as the starting material, the disulfide‐mediated reversible polymerization and acylhydrazone‐based dynamic covalent crosslinking can be combined in a one‐pot solvent‐free reaction, resulting in mechanically robust, tough, and processable crosslinked materials. The dynamic covalent bonds in both backbones and crosslinkers endow the network with depolymerization capability under mild conditions and, importantly, virgin‐quality monomers can be recovered and separated. This proof‐of‐concept study show opportunities to design chemically recyclable materials based on the dynamic chemistry toolbox.
An Organic Laser Based on Thermally Activated Delayed Fluorescence with Aggregation‐Induced Emission and Local Excited State Characteristics
Authors: Li Shuai , Chen Jingyao , Wei Yuling , De Jianbo , Geng Hua , Liao Qing , Chen Runfeng , Fu Hongbing 
Published: August 2022

AbstractThe spatial separation between the highest occupied and the lowest unoccupied molecular orbitals (HOMO and LUMO) in thermally activated delayed fluorescent (TADF) molecules leads to charge transfer (CT) states, which degrade the oscillator strength of emission transition and sacrifices high solid‐state photoluminescence quantum yield (PLQY), together limiting its application in organic solid‐state lasers (OSSLs). Here, we demonstrated organic microwire lasers from TADF emitters that combine aggregation induced emission (AIE) and local excited (LE) state characteristics. The unique AIE and LE feature lead to a PLQY approaching 50 % and a high optical gain of 870 cm−1 for TADF microwires. The regenerated singlet excitons by reverse intersystem crossing (RISC) process are conducive to population inversion. As a result, we demonstrated microwire lasers around 465 nm with a low threshold of 3.74 μJ cm−2. Therefore, our work provides insight to design TADF materials for OSSLs.
Synthesis of a Hexachloro Sulfate(IV) Dianion Enabled by Polychloride Chemistry
Authors: Voßnacker Patrick , Wüst Alisa , Müller Carsten , Kleoff Merlin , Riedel Sebastian 
Published: August 2022

AbstractThe preparation and structural characterization of [NEt3Me]2[SCl6] is described, which is the first example of a [SCl6]2− dianion and of a halosulfate anion of the type [SxXy]z− in general. This dianion belongs to the group of 14‐valence electron AB6E systems and forms an octahedral structure in the solid‐state. Interestingly, co‐crystallization with CH2Cl2 affords [NEt3Me]2[SCl6]⋅4 CH2Cl2 containing [SCl6]2− dianions with C4v symmetry. As suggested by quantum‐chemical calculations, the distortion of the structure is not caused by a stereochemically active lone pair but by enhanced hydrogen bonding interactions with CH2Cl2. At elevated temperatures, [NEt3Me]2[SCl6] decomposes to various sulfur chlorine compounds as shown by Raman spectroscopy. Cooling back to room temperature results in the selective formation of [NEt3Me]2[SCl6] which is comparable to the well‐studied SCl4.
Megalo‐Cavitands: Synthesis of Acridane[4]arenes and Formation of Large, Deep Cavitands for Selective C70 Uptake
Authors: Pfeuffer‐Rooschüz Jonathan , Heim Salome , Prescimone Alessandro , Tiefenbacher Konrad 
Published: August 2022

AbstractDeep cavitands, concave molecular containers, represent an important supramolecular host class that has been explored for a variety of applications ranging from sensing, switching, purification and adsorption to catalysis. A major limitation in the field has been the cavitand volume that is restricted by the size of the structural platform utilized (diameter approx. 7 Å). We here report the synthesis of a novel, unprecedentedly large structural platform, named acridane[4]arene (diameter approx. 14 Å), suitable for the construction of cavitands with volumes of up to 814 Å3. These megalo‐cavitands serve as size‐selective hosts for fullerenes with mM to sub‐μM binding affinity for C60 and C70. Furthermore, the selective binding of fullerene C70 in the presence of C60 was demonstrated.
Selection of promising lines for yield and quality traits in advanced segregating generation of linseed
Authors: Abtahi Mozhgan , Mirlohi Aghafakhr , Zare Sara 
Published: August 2022

AbstractLinseed (Linum usitatissimum L.) is becoming more important due to its unique nutrient profile and a source of high‐added value raw material, for both food and industrial uses. However, low productivity and lack of combined quality traits has limited its cultivation and there is an urgent need to develop improved varieties through genetic recombination of traits. In this respect 96 linseed F4 families, derived from eight contrasting parents were field evaluated during 2019–2020. A reasonable diversity among the F4 families indicated a considerable potential for improving linseed for agronomic and quality traits. Results demonstrated that strict selection for oil content, protein content, fatty acid composition and amino acid profile, with comparatively high heritability and genetic advance, is feasible and successful in F4 generation. Families with linolenic acid content as low as 9.26% and as high as 72.46% were identified. Yellow‐seeded families had higher values of phenological traits, plant height and number of capsules and lower values of seed number, linolenic acid, palmitic acid, stearic acid, aspartic acid, leucine and lysine content than the brown‐seeded types. Among the many low linolenic acid families identified those with superior yield and quality traits, offer opportunitiesfor development of new varieties that may be of high value in food industry. Also the high linolenic acid and high oil content families recognized may have genetic potentials for development of new varieties of linseed for industrial purposes. Among the parental genotypes four were found to be promising for developing superior high yielding linseeds with high quality.
Effects of triglycidyl isocyanurate on thermal, mechanical, and gas barrier properties of poly(butylene adipate‐co‐terephthalate)/poly(propylene carbonate) composites
Authors: Xie Dong , Pang Qiyao , Zhao Yang , Li Yuan , Li Fayong , He Hui 
Published: August 2022

AbstractThe gas barrier properties of poly(butylene adipate‐co‐terephthalate) (PBAT) films can be improved with poly(propylene carbonate) (PPC), but this will reduce the mechanical properties. In this work, PBAT/PPC composites and the related films were prepared by melt blending followed by film blowing process using triglycidyl isocyanurate (TGIC) as the reactive compatibilizer. Herein, the structure, thermal properties, mechanical properties, and gas barrier properties of the composites were systematically characterized via various techniques. The results indicated that the incorporation of TGIC effectively improved the interfacial compatibility between PBAT and PPC, and enhanced the thermal stability of the composites, especially for PPC. In addition, PBAT/PPC/TGIC films at 1 phr (parts per hundreds of resin) TGIC content exhibited a tensile strength of 30.8 MPa, and an elongation at break of 860%, which are 136% and 142% of those of PBAT/PPC, respectively. Meanwhile, the water vapor transmission rate dropped by 33% at this content. The improvement of mechanics and gas barrier properties makes PBAT/PPC film better meet the requirements of food preservation packaging such as fruits and vegetables.
Technology follows Construction – Potenziale von Lowtech‐Gebäuden
Authors: Senkel Carolin , Otto Jens 
Published: August 2022

AbstractModerne energieeffiziente Gebäude definieren sich über einen hohen Grad an verbauter Technik. Durch deren vielseitigen Einsatz werden solche Gebäude als komfortabel und qualitativ hochwertiger empfunden. Auch die gesetzlichen Vorgaben und Förderungen lenken den Trend zukünftiger Gebäude hin zu einem hohen Grad energieeffizienter Technik. Dabei gilt jedoch der Leitsatz: Die beste Energie ist die, die erst gar nicht verbraucht wird. Um vor allem auch der grauen Energie Rechnung zu tragen und tatsächlich nachhaltige, zukunftsfähige Gebäude entstehen zu lassen, sollte ein Paradigmenwechsel eingeleitet werden hin zur Suffizienz. Ein Trend ist dabei besonders hervorzuheben – die Lowtech‐Gebäude. Sie folgen dem Grundsatz, zuerst die Potenziale der Baukonstruktion bauphysikalisch voll auszuschöpfen und danach die benötigte Restenergie durch Technik zu ergänzen. Definiert werden könnten sie durch den Leitsatz: Technology follows Construction. Lowtech‐Gebäude sind aber nicht nur im Kontext des Klimawandels vorteilhaft, sie bieten außerdem wirtschaftliche Lösungsansätze für Herausforderungen wie die gesellschaftliche Akzeptanz energieeffizienter Maßnahmen, die soziale Nachhaltigkeit und die Post‐Pandemie. Dank der zunehmenden Anzahl erfolgreicher Praxisprojekte gewinnen Lowtech‐Gebäude an Bedeutung.
Messtechnische Untersuchung der Auswirkung von Fassadenbegrünungen auf den U‐Wert der Außenwand
Authors: Alsaad Hayder , Engelhardt Miriam , Völker Conrad 
Published: August 2022

AbstractDie kühlende Wirkung von Fassadenbegrünung wird in der Literatur häufig als ein Ansatz zur Bekämpfung des Klimawandels und der erhöhten Temperaturen im Sommer diskutiert. Neben diesem Effekt können Fassadenbegrünungen auch im Winter eine Dämmwirkung entfalten. In dieser Studie wurden die Auswirkungen eines Fassadenbegrünungsmoduls auf den Wärmetransport durch die dahinter stehende Außenwand während der Heizperiode untersucht. Dafür wurden empirische Messungen an einem Prototyp eines Begrünungsmoduls an einem Testcontainer durchgeführt. Zu den gemessenen Parametern gehörten die Oberflächen‐ und Lufttemperatur (jeweils innen und außen) und die Wärmestromdichte durch den Wandaufbau. Die Messungen wurden an zwei verschiedenen Stellen durchgeführt: ohne Begrünung (Referenzwand) und mit Begrünung. Der Wärmedurchgangskoeffizient der Fassade wurde für beide Stellen nach drei verschiedenen Datenfilterungsmethoden berechnet. Die Ergebnisse zeigen, dass das Fassadenbegrünungsmodul den Wärmetransport durch die Wand reduziert. Je nach verwendeter Filterungsmethode ergibt sich durch die Fassadenbegrünung eine Reduktion des Wärmedurchgangskoeffizienten des Wandaufbaus um 9 % bis 18 %.
Einsatz von Computerprogrammen in der Hochschullehre– Serie: Gebäudesimulation und Berechnungstools in der Lehre
Authors: Voss Karsten , Kalpkirmaz Rizaoglu Isil 
Published: August 2022

AbstractDiese Artikelserie stellt den Einsatz von Computerprogrammen in der Hochschullehre der Bauphysik und Gebäudetechnik für Architekten und Bauingenieure vor.In diesem Beitrag werden die Motivation zur Artikelserie und die Ergebnisse einer Online‐Umfrage an die Lehrenden der deutschsprachigen Hochschulen, initiiert und durchgeführt vom Fachgebiet Bauphysik und Technische Gebäudeausrüstung der Universität Wuppertal, aufgeführt.
Variable selection for nonparametric additive Cox model with interval‐censored data
Authors: Tian Tian , Sun Jianguo 
Published: August 2022

AbstractThe standard Cox model is perhaps the most commonly used model for regression analysis of failure time data but it has some limitations such as the assumption on linear covariate effects. To relax this, the nonparametric additive Cox model, which allows for nonlinear covariate effects, is often employed, and this paper will discuss variable selection and structure estimation for this general model. For the problem, we propose a penalized sieve maximum likelihood approach with the use of Bernstein polynomials approximation and group penalization. To implement the proposed method, an efficient group coordinate descent algorithm is developed and can be easily carried out for both low‐ and high‐dimensional scenarios. Furthermore, a simulation study is performed to assess the performance of the presented approach and suggests that it works well in practice. The proposed method is applied to an Alzheimer's disease study for identifying important and relevant genetic factors.
Multimodular vascularized bone construct comprised of vasculogenic and osteogenic microtissues
Authors: Schott Nicholas G. , Vu Huy , Stegemann Jan P. 
Published: August 2022

AbstractBioengineered bone designed to heal large defects requires concomitant development of osseous and vascular tissue to ensure engraftment and survival. Adult human mesenchymal stromal cells (MSC) are promising in this application because they have demonstrated both osteogenic and vasculogenic potential. This study employed a modular approach in which cells were encapsulated in biomaterial carriers (microtissues) designed to support tissue‐specific function. Osteogenic microtissues consisting of MSC embedded in a collagen‐chitosan matrix; vasculogenic (VAS) microtissues consisted of endothelial cells and MSC in a fibrin matrix. Microtissues were precultured under differentiation conditions to induce appropriate MSC lineage commitment, and were then combined in a surrounding fibrin hydrogel to create a multimodular construct. Results demonstrated the ability of microtissues to support lineage commitment, and that preculture primes the microtissues for the desired function. Combination of osteogenic and vasculogenic microtissues into multimodular constructs demonstrated that osteogenic priming resulted in sustained osteogenic activity even when cultured in vasculogenic medium, and that vasculogenic priming induced a pericyte‐like phenotype that resulted in development of a primitive vessel network in the constructs. The modular approach allows microtissues to be separately precultured to harness the dual differentiation potential of MSC to support both bone and blood vessel formation in a unified construct.
Fabrication and in vitro evaluation of 3D printed porous silicate substituted calcium phosphate scaffolds for bone tissue engineering
Authors: Chen Dechun , Chen Guanghua , Zhang Xin , Chen Jingtao , Li Jinmeng , Kang Kunlong , He Weitao , Kong Yuanhang , Wu Leilei , Su Bo , Zhao Kui , Si Daiwei , Wang Xintao 
Published: August 2022

AbstractSilicate‐substituted calcium phosphate (Si‐CaP) ceramics, alternative materials for autogenous bone grafting, exhibit excellent osteoinductivity, osteoconductivity, biocompatibility, and biodegradability; thus, they have been widely used for treating bone defects. However, the limited control over the spatial structure and weak mechanical properties of conventional Si‐CaP ceramics hinder their wide application. Here, we used digital light processing (DLP) printing technology to fabricate a novel porous 3D printed Si‐CaP scaffold to enhance the scaffold properties. Scanning electron microscopy, compression tests, and computational fluid dynamics simulations of the 3D printed Si‐CaP scaffolds revealed a uniform spatial structure, appropriate mechanical properties, and effective interior permeability. Furthermore, compared to Si‐CaP groups, 3D printed Si‐CaP groups exhibited sustained release of silicon (Si), calcium (Ca), and phosphorus (P) ions. Furthermore, 3D printed Si‐CaP groups had more comprehensive and persistent osteogenic effects due to increased osteogenic factor expression and calcium deposition. Our results show that the 3D printed Si‐CaP scaffold successfully improved bone marrow mesenchymal stem cells (BMSCs) adhesion, proliferation, and osteogenic differentiation and possessed a distinct apatite mineralization ability. Overall, with the help of DLP printing technology, Si‐CaP ceramic materials facilitate the fabrication of ideal bone tissue engineering scaffolds with essential elements, providing a promising approach for bone regeneration.