bluuebunny/crossref_metadata_2025_split huggingface dataset:
Thickening of Isolated and Multilayered Crystals and Its Implications on Melting Kinetics; The Role of Inter‐ and intra‐crystalline Regions
Authors: Rastogi Sanjay , Romano Dario 
Published: March 2022

Abstract
Melting of crystalline region in a semicrystalline polymer is a complex phenomenon, which is strongly influenced by the topological constraints present in the noncrystalline region. In an isolated crystal, detachment of chain stems from its crystalline surface can occur in succession or in cluster. The difference in detachment of the chain stems strongly depends on the topological constraints of the chain segments on the fold surface. Successive detachment of the chain stems, observed on melting of crystals while annealing at the onset of the peak melting temperature, appears to occur when chain folding is facilitated by adjacent reentry. In the annealing process, no crystal thickening in isolated crystals, having molar mass sufficiently high to suppress the effect of chain ends, is observed, as the crystal thickening will require cooperative chain mobility of the chain stems within the crystal linked by the chain segments in the fold. Retrospectively, because of the possibility of successive chain detachment, melting temperature decreases with decreasing heating rate, contradicting the assumption of increase in melting temperature on annealing. In the isolated crystals, having complex reentrant chains on the fold surface, successive detachment of chains from a crystal surface is frustrated, and cluster melting is promoted. Such crystals, though isolated, do not show melting on annealing. However, in contrast to the isolated crystals, in multilayered crystals instead of melting on annealing at the onset melting temperature, crystal thickening will occur that would cause increase in the melting temperature. This thickening process is facilitated, as it requires the localized motion only rather than the cooperative motion of the chain stems within the crystals. Thickening in the isolated crystals, if observed during polymerization or due to the appearance of a transient mobile phase, is referred as the primary thickening, whereas the crystal thickening in the multilayered crystals is called the secondary thickening.
Nonequilibrium Properties of Thin Polymer Films
Authors: Chandran Sivasurender , Reiter Günter 
Published: March 2022

AbstractRapid industrial processes often freeze polymers in nonequilibrium conformations, which, in turn, cause material properties that are significantly different from the predictions of equilibrium theories. Such deviations in properties may introduce enhanced material performance. Thus, by choosing appropriate processing pathways, we potentially can control macroscopic properties and performance of polymers. However, due to our current lack of fundamental understanding of the behavior of nonequilibrated polymers, we have to rely on empirical knowledge, imposing trial‐and‐error approaches for achieving desired properties. Considering these aspects, we discuss recent studies on polymer films revealing that quantitative relations exist between properties and processing pathways, suggesting possible relations for processing‐induced deviations in chain conformations. These relations propose that long‐living and long‐ranged correlations between polymers have been induced by processing, as indicated by the observation of relaxation times much longer than known for equilibrated polymers. We present an example where control of processing conditions for thin films allowed to translate the molecular relaxations during equilibration into a predictable lifting of macroscopic loads. Motivated by the presented results, we conclude that a comprehensive understanding of polymers with nonequilibrium conformations may not only expand the available spectrum of polymer properties but will also widen the scope of polymer science.
Broadband Dielectric Spectroscopy and Its Application in Polymeric Materials
Authors: Popov Ivan , Cheng Shiwang , Sokolov Alexei P. 
Published: March 2022

AbstractRelaxation processes in polymeric systems span over an extremely wide range of time scales. There are a few experimental techniques capable of covering such a range, and one of the most versatile of them is Broadband Dielectric Spectroscopy (BDS). Current BDS covers an enormous frequency range, from ∼10−5to ∼1012 Hz, enabling a practical study of the full spectrum of relaxation phenomena in a broad temperature and pressure range without involvement of time‐temperature superposition. In this article, we present capabilities of the BDS technique on examples of different polymeric systems and explain what kind of information can be extracted from the frequency spectra of the dielectric permittivity and conductivity. We present examples of dielectric studies of segmental and chain dynamics, secondary relaxations, explain additional phenomena in multicomponent systems (e.g. polymer nanocomposites and block copolymers), and discuss specifically examples of ion‐conducting polymers. We emphasize that BDS does not probe molecular motions directly and measures fluctuations of dipoles or diffusion of charges. So, combination of BDS with other experimental techniques is the best approach to study dynamics of various materials.
Pickering Emulsions as Designer Platforms for Polymer‐Based Hybrid Materials: Routes to Controlled Structures
Authors: Zhang Yunchong , Cheng Huan , Li Xiang , Wang Bijia , Feng Xueling , Mao Zhiping , Vancso G. Julius , Sui Xiaofeng 
Published: March 2022

Abstract
Polymer‐based hybrid materials have attracted great interest in academic research and industry because they can effectively combine the advantages of their different components. Pickering emulsions as designer platforms provide a very efficient and often unappreciated route to prepare polymer‐based hybrids. Their applications cover a broad range, including filter media, ion exchange modules, monolithic polymer supports for catalysis, covalent enzyme immobilization, and even scaffolds for tissue engineering. In this article, we first provide an introduction to the basics and formation of Pickering emulsions and then discuss how these systems can be used to obtain templates for the fabrication of materials with various morphologies, such as microspheres, fibers, films, and porous matrices. We then discuss the uniqueness of Pickering systems for morphology control and the resulting added value to obtain advanced complex and hybrid materials. We then review and summarize recent advances in the preparation approaches (polymerization and solvent evaporation) and physical morphologies (microspheres, fibers, films, and porous matrices). Finally, we offer an outlook for future developments.
Rheology of Unentangled Polymer Solutions Depends on Three Macromolecular Properties: Flexibility, Extensibility, and Segmental Dissymmetry
Authors: Dinic Jelena , Martínez Narváez Carina D. V. , Sharma Vivek 
Published: March 2022

AbstractWe elucidate the influence of chemical structure on macromolecular hydrodynamics and rheological response using poly(ethylene oxide) or PEO and 2‐hydroxyethyl cellulose (HEC). We contrast the shear rheology response measured using torsional rheometry and find the wellknown universalities like comparable shear viscosity for dilute solutions at comparable degree of chain overlap. We show that dripping‐onto‐substrate (DoS) rheometry protocols that we developed facilitate characterization of pinching dynamics and extensional rheology response even for weakly elastic, low viscosity fluids. Even for unentangled solutions with comparable shear viscosity and molecular weights, the PEO solutions exhibit distinctively higher values of extensional relaxation time, extent of strain hardening, transient extensional viscosity, and an overall delay in pinch‐off. We find that the extensional relaxation times exhibit concentration dependence distinct from shear rheology response, or anticipated by blob models, developed for relaxation of weakly perturbed chains. Most significantly, we show that the influence of polymer choice can be evaluateda priori, using three macromolecular parameters: flexibility, extensibility, and segmental dissymmetry, defined as the ratio of Kuhn length to packing length. We identify the minimum concentration above which elastocapillary response appears and define a stretched overlap concentration below which the extensional relaxation time is concentration independent.
Neurofilament light chain and retinal layers' determinants and association: A population‐based study
Authors: Garzone Davide , Finger Robert P. , Mauschitz Matthias M. , Santos Marina L. S. , Breteler Monique M. B. , Aziz N. Ahmad 
Published: March 2022

AbstractBoth retinal atrophy measured through optical coherence tomography and plasma neurofilament light chain (NfL) levels are markers of neurodegeneration, but their relationship is unknown. Therefore, we assessed their determinants and association in 4369 participants of a population‐based study. Both plasma NfL levels and inner retinal atrophy increased exponentially with age. In the presence of risk factors for neurodegeneration (including age, smoking, and a history of neurological disorders), plasma NfL levels were associated with inner retinal atrophy and outer retinal thickening. Our findings indicate that inner retinal atrophy can reflect neuroaxonal damage as mirrored by rising plasma NfL levels.
Personalized Risk Model and Leveraging of Magnetic Resonance Imaging–Based Structural Phenotypes and Clinical Factors to Predict Incidence of Radiographic Osteoarthritis
Authors: Lee Jinhee J. , Namiri Nikan K. , Astuto Bruno , Link Thomas M. , Majumdar Sharmila , Pedoia Valentina 
Published: March 2022

ObjectiveOur study aimed to investigate the association between time to incidence of radiographic osteoarthritis (OA) and magnetic resonance imaging (MRI)–based structural phenotypes proposed by the Rapid Osteoarthritis MRI Eligibility Score (ROAMES).MethodsA retrospective cohort of 2,328 participants without radiographic OA at baseline were selected from the Osteoarthritis Initiative study. Utilizing a deep‐learning model, we automatically assessed the presence of inflammatory, meniscus/cartilage, subchondral bone, and hypertrophic phenotypes from MRIs acquired at baseline and 12‐, 24‐, 36‐, 48‐, 72‐, and 96‐month follow‐up visits. In addition to 4 structural phenotypes, we examined severe knee injury history and Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC) pain scores as time dependent. We used Cox proportional hazards regression to analyze the association between 4 structural phenotypes and radiographic OA disease‐free survival, both univariate and adjusted for known risk factors including age, sex, race, body mass index, presence of Heberden's nodes, and knee malalignment.ResultsInflammatory (hazard ratio [HR] 3.37 [95% confidence interval (95% CI) 2.45–4.63]), meniscus/cartilage (HR 1.55 [95% CI 1.21–1.98]), and subchondral bone (HR 1.84 [95% CI 1.63–2.09]) phenotypes were associated with time to radiographic OA at P < 0.05 when adjusted for the risk factors. Sex was a modifier of hypertrophic phenotype association with time to radiographic OA. Female participants with the hypertrophic phenotype were associated with 2.8 times higher risk of radiographic OA (95% CI 2.25–7.54) compared to male participants without the hypertrophic phenotype.ConclusionFour ROAMES phenotypes may contribute to time to radiographic OA incidence and if validated could be used as a promising tool for personalized OA management.
Synergistic Solvation and Interface Regulations of Eco‐Friendly Silk Peptide Additive Enabling Stable Aqueous Zinc‐Ion Batteries
Authors: Wang Baojun , Zheng Rong , Yang Wei , Han Xin , Hou Chengyi , Zhang Qinghong , Li Yaogang , Li Kerui , Wang Hongzhi 
Published: March 2022

AbstractAqueous Zn‐ion batteries have aroused much attention recently, yet challenges still exist in the lack of low‐cost, highly stable electrolytes to tackle the serious side reactions at Zn anode–electrolyte interface. Herein, a ZnSO4‐based low‐cost aqueous electrolyte is demonstrated with a small amount of eco‐friendly silk peptide as an efficient additive. Compared with silk sericin and fibroin, silk peptide with abundant strong polar groups (COOH and NH2) suppresses the side reactions. Namely, silk peptide regulates the solvation structure of Zn2+ to decrease coordinated active H2O and SO42−, and tends to anchor on Zn anode surface for the isolation of contact H2O/SO42− as well as electrostatic shielding, demonstrating synergistic solvation and interface regulating effect. Consequently, the excellent cycle life (3000 h) and Coulombic efficiency (99.7%) of Zn anodes are revealed in 2 m ZnSO4 electrolyte with only 5 mg mL−1 of silk peptide (≈0.49 USD L−1), promising practical applications of reversible zinc‐ion batteries.
The Influence of Surface Chemistry on Critical Current Density for Garnet Electrolyte
Authors: Chen Shaojie , Nie Zhiwei , Tian Feifei , Nie Lu , Wei Ran , Yu Jiameng , Gao Tianyi , Sun Zhaoru , Yang Nan , Liu Wei 
Published: March 2022

AbstractGarnet‐based solid state lithium batteries have attracted a lot of attention due to their potential advantages in safety and energy density. However, the high electrode–electrolyte interfacial resistance and low critical current density (CCD) related with lithium dendrite penetration have seriously hindered their further development and practical application. Here, for garnet‐type solid electrolyte, the surface Li2CO3, interlayer species, lithium wettability, interfacial impedance, and CCD are systematically investigated. It turns out that Li2CO3‐free garnet electrolyte is intrinsically lithiophilic, and the interfacial impedance is mainly affected by the amount of surface Li2CO3. In addition, the CCD values are manipulated by the interfacial impedance rather than the apparent Li wettability. This study provides a comprehensive understanding about the interrelationships among surface chemistry, lithium wettability, interfacial impedance, and critical current density for garnet‐type solid electrolytes.
Surfactant‐Inspired Coassembly Strategy to Integrate Aggregation‐Induced Emission Photosensitizer with Organosilica Nanoparticles for Efficient Theranostics
Authors: Yan Saisai , Sun Panpan , Niu Niu , Zhang Zhijun , Xu Weilin , Zhao Siyi , Wang Lei , Wang Dong , Tang Ben Zhong 
Published: March 2022

AbstractConstruction of versatile nanotemplate bearing inherent distinctive functions and prominent drug‐carrying capability is an appealing yet significantly challenging task. Here, inspired by the guiding role of surfactant in preparing nanoparticles, an amphiphilic aggregation‐induced emission (AIE) photosensitizer, namely MeOTTVP, is synthesized with attractive near‐infrared (NIR) emission and high‐performance reactive oxygen species production, and followed by dual‐templating‐assisted one‐pot method involving MeOTTVP as the skeleton to fabricate organosilica nanoparticles (AIE‐ONs). The presented AIE‐ONs perfectly inherit the functions of MeOTTVP, and are also capable of loading antibiotics and anticancer drugs. Doxorubicin can be assembled on AIE‐ONs and then capped with hyaluronic acid, endowing the resulting hybrid with NIR fluorescence imaging‐guided synergetic photodynamic/chemotherapy performance, thereby offering boosted anticancer efficacy and reduced side effects. Furthermore, by loading antibiotic rifampicin, the newly obtained AIE‐ONs integrating chemo‐photodynamic antibacterial functions provide broad‐spectrum antibacterial activity and fluorescence monitoring behavior. This study thus not only offers a promising strategy to fabricate NIR nanoparticles on a large scale, but also provides useful insights into designing an advanced theranostic protocol for treating both cancer and bacterial infections.
Electrochemical Thin‐Film Transistors using Covalent Organic Framework Channel
Authors: Hota Mrinal K. , Chandra Suman , Lei Yongjiu , Xu Xiangming , Hedhili Mohamed N. , Emwas Abdul‐Hamid , Shekhah Osama , Eddaoudi Mohamed , Alshareef Husam N. 
Published: March 2022

AbstractCovalent organic framework (COF) thin films have been successfully prepared and utilized as a channel material in electrical double‐layer (EDL) electrochemical transistors. 4,4′‐azodianiline (Azo) and 1,3,5‐triformylphloroglucinol(Tp) precursors are introduced to prepare azo (NN) functionalized ß‐keto‐enamine COF (Tp‐Azo) thin films. The EDL transistor exhibits a switching ratio of 103 times, a low threshold voltage of 0.6 V, and a field‐effect mobility of 0.53 cm2 V−1 s−1. The dynamic behavior of the transistor under different input signals shows responses, which are very similar to the biological synaptic behavior, indicating that the COF devices can be used as artificial synapses. This report opens a new direction in covalent–organic framework development in iontronic applications.
Bioinspired Phototropic MXene‐Reinforced Soft Tubular Actuators for Omnidirectional Light‐Tracking and Adaptive Photovoltaics
Authors: Yang Mengyuan , Xu Yiyi , Zhang Xuan , Bisoyi Hari Krishna , Xue Pan , Yang Yanzhao , Yang Xiao , Valenzuela Cristian , Chen Yuanhao , Wang Ling , Feng Wei , Li Quan 
Published: March 2022

AbstractEndowing artificial advanced materials and systems with biomimetic self‐regulatory intelligence is of paramount significance for the development of somatosensory soft robotics and adaptive optoelectronics. Herein, a bioinspired phototropic MXene‐reinforced soft tubular actuator is reported that exhibits omnidirectional self‐orienting ability and is capable of quickly sensing, continuously tracking, and adaptively interacting with incident light in all zenithal and azimuthal angles of 3D space. The novelty of the soft tubular actuator lies in three aspects: 1) the new polymerizable MXene nanomonomer shows high compatibility with liquid crystal elastomer (LCE) matrices and can be in situ photopolymerized into the polymer networks, thus enhancing the mechanical and photoactuation properties; 2) the distinct hollow and radially symmetrical structure facilitates the actuator with fast photoresponsiveness and phototropic performance through retarding the heat conduction along the radial direction; 3) the MXene‐LCE soft tubular actuator simultaneously integrates sensing, actuation, and built‐in feedback loop, thus leading to a high light‐tracking accuracy and adaptive phototropism like a hollow stem of plants in nature. As a proof‐of‐concept demonstration, an adaptive photovoltaic system with solar energy harvesting maximization is illustrated. This work can provide insights into the development of artificial intelligent materials toward adaptive optoelectronics, intelligent soft robotics, and beyond.
Ultrasensitive Airflow Sensors Based on Suspended Carbon Nanotube Networks
Authors: Jiang Qinyuan , Li Run , Wang Fei , Shi Xiaofei , Chen Fengxiang , Huang Ya , Wang Baoshun , Zhang Wenshuo , Wu Xueke , Wei Fei , Zhang Rufan 
Published: March 2022

AbstractHigh‐performance airflow sensors are in great demand in numerous fields but still face many challenges, such as slow response speed, low sensitivity, large detection threshold, and narrow sensing range. Carbon nanotubes (CNTs) exhibit many advantages in fabricating airflow sensors due to their nanoscale diameters, excellent mechanical and electrical properties, and so on. However, the intrinsic extraordinary properties of CNTs are not fully exhibited in previously reported CNT‐based airflow sensors due to the mixed structures of macroscale CNT assemblies. Herein, this article presents suspended CNT networks (SCNTNs) as high‐performance airflow sensors, which are self‐assembled by ultralong CNTs and short CNTs in a one‐step floating catalyst chemical vapor deposition process. The SCNTN‐based airflow sensors achieved a record‐breaking short response time of 0.021 s, a high sensitivity of 0.0124 s m−1, a small detection threshold of 0.11 m s−1, and a wide detection range of ≈0.11–5.51 m s−1, superior to most of the state‐of‐the‐art airflow sensors. To reveal the sensing mechanism, an acoustic response testing system and a mathematical model are developed. It is found that the airflow‐caused intertube stress change resulted in the resistance variation of SCNTNs.
Aggregation Control, Surface Passivation, and Optimization of Device Structure toward Near‐Infrared Perovskite Quantum‐Dot Light‐Emitting Diodes with an EQE up to 15.4%
Authors: Tseng Zong‐Liang , Chen Lung‐Chien , Chao Li‐Wei , Tsai Meng‐Ju , Luo Dian , Al Amin Nurul Ridho , Liu Shun‐Wei , Wong Ken‐Tsung 
Published: March 2022

AbstractIn recent years, the performance of perovskite quantum dots (QDs) and QD‐based light‐emitting diodes (QLEDs) has improved greatly, with electroluminescence (EL) efficiency of green and red emission exceeding 20%. However, the development of perovskite near‐infrared (NIR) QLEDs has reached stagnation, where the reported maximum EL efficiency is still below 6%, limiting their further applications. In this work, new NIR‐emissive FAPbI3 QDs are developed by post‐treating long alkyl‐encapsulated QDs with 2‐phenylethylammonium iodide (PEAI). The incorporation of PEAI reduces the QD surface defects for giving a high photoluminescence quantum yield up to 61.6%. The n‐octane solution of PEAI‐passivated FAPbI3 QDs is spin coated on top of the PEDOT:PSS‐treated ITO electrode modified with a thermally crosslinked hole‐transporting layer to give a full‐coverage, smooth, and dense QD film. Incorporating with an effective electron‐transporting material, CN‐T2T, which has deep lowest unoccupied molecular orbital and good electron mobility, the optimal device with EL λmax at 772 nm achieves an external quantum efficiency up to 15.4% at a current density of 0.54 mA cm−2 (2.6 V), which is the highest efficiency ever reported for perovskite‐based NIR QLEDs. This study provides a facile strategy to prepare high‐quality perovskite QD films suitable for highly efficient NIR QLED applications.
Sperm Syringe: 3D Sorting Platform for Assisted Reproduction
Authors: Yazdan Parast Farin , O'Bryan Moira K. , Nosrati Reza 
Published: March 2022

AbstractSelection of high‐quality sperm is crucial to assisted reproduction. However, conventional clinical methods for sperm selection are manual and prone to operator errors. This article presents ‘sperm syringe', a scalable technology that mimics the highly parallelized 3D selection process in vivo via a 3D network of 560 microchannels to select high‐quality sperm. Sperm syringe retrieves more than 41% of healthy sperm from the initial sperm sample in under 15 min, providing a sufficient volume (≈500 µL) and number (1,600,000) of high‐quality sperm for fertility treatments. Experiments with bull and human sperm indicate 65% improvement in selected sperm morphology and DNA integrity, considerably outperforming the current best clinical practices. This approach enables the selection of a subpopulation of high‐quality human sperm from an oligozoospermia sample with DNA integrity below the reference value for fertility. The fabrication method of the device is also simple and scalable, representing a commercially viable technology for translation and clinical adoption. Sperm syringe provides a promising opportunity for clinics to use less invasive assisted reproductive technologies (ARTs) over intracytoplasmic sperm injection, thus reducing the associated clinical workload and optimizing long‐term health outcomes for ART‐conceived children.