bluuebunny/crossref_metadata_2025_split huggingface dataset:
Near‐Field Coupling of Janus Dipoles Beyond Polarization Locking
Authors: Wang Chan , Zhong Yuhan , Chen Xuhuinan , Wang Huaping , Low Tony , Chen Hongsheng , Zhang Baile , Lin Xiao 
Published: May 2024

AbstractPolarization, as a fundamental property of light, plays a key role in many phenomena of near‐field coupling, namely the coupling of source's evanescent waves into some guided modes. As a typical example of the polarization‐locked phenomenon in the near‐field coupling, the Janus dipole has the orientation of its near‐field coupling face intrinsically determined by the polarization state of linearly‐polarized surface waves, specifically whether they are transverse‐magnetic (TM) or transverse‐electric (TE) surface waves. Here, a mechanism to achieve the directional near‐field coupling of Janus dipoles beyond polarization locking by leveraging hybrid TM‐TE surface waves is presented. These hybrid surface waves, as eigenmodes with both TM and TE wave components, can be supported by optical interfaces between different filling materials inside a parallel‐plate waveguide. Under the excitation of hybrid surface waves, it is found that the coupling and non‐coupling face of a Janus dipole may be switched, if the Janus dipole itself rotates in a plane parallel to the designed optical interface between different filling materials, without resorting to the change of surface‐wave polarization. The underlying mechanism is due to the capability of hybrid surface waves to extract both the source's TM and TE evanescent waves, which offers an alternative paradigm to regulate the interference in the near‐field coupling.
Hybrid Single Crystals of Poly(ε‐caprolactone) Homopolymers and Poly(ε‐caprolactone)‐b‐Poly(ethylene oxide) Block Copolymers
Authors: Yang Chen , Li Zi‐Xian , Xu Jun‐Ting 
Published: May 2024

AbstractHybrid single crystals (HSCs) of different poly(ε‐caprolactone) (PCL) homopolymers with a poly(ε‐caprolactone)‐b‐poly(ethylene oxide) (PCL‐b‐PEO) block copolymer (BCP) are prepared. The effects of PCL length, PCL/PCL‐b‐PEO molar ratio, crystallization temperature (Tc), and solvent on crystal morphology are investigated. The optimal Tc for the formation of more perfect HSCs is between those for homocrystals of individual PCL and PCL‐b‐PEO and roughly increases with the length of PCL and PCL/PCL‐b‐PEO molar ratio. The chain folding in the HSCs is studied by comparing the experimentally measured heights obtained by atomic force microscopy (AFM) and theoretically calculated ones based on a sandwich structure model. Under most situations, the PCL homopolymers adopt a larger chain folding number in the HSCs than that in their homocrystals, while the chain folding of BCP remains unaltered. However, when both PCL homopolymer and PCL‐b‐PEO BCP crystallize slowly and the overcrowding of the PEO is effectively alleviated, thicker HSCs can be formed, in which the PCL homopolymer preserves the chain folding in its homocrystals but the BCP adopts a reduced chain folding number as compared with that in its homocrystals. The relative crystallization rate of PCL homopolymer versus BCP also affects the real composition and overall height of the HSCs.
High Glass Transition Temperature Fluorinated Polymers Based on Transfer Learning with Small Experimental Data
Authors: Yang Jin‐Hoon , Lee Jiyoung , Kwon Hajin , Sohn Eun‐Ho , Chang Hyunju , Jang Seunghun 
Published: May 2024

AbstractMachine learning can be used to predict the properties of polymers and explore vast chemical spaces. However, the limited number of available experimental datasets hinders the enhancement of the predictive performance of a model. This study proposes a machine learning approach that leverages transfer learning and ensemble modeling to efficiently predict the glass transition temperature (Tg) of fluorinated polymers and guide the design of high Tg copolymers. Initially, the quantum machine 9 (QM9) dataset is employed for model pretraining, thus providing robust molecular representations for the subsequent fine‐tuning of a specialized copolymer dataset. Ensemble modeling is used to further enhance prediction robustness and reliability, effectively addressing the problems owing to the limited and unevenly distributed nature of the copolymer dataset. Finally, a fine‐tuned ensemble model is used to navigate a vast chemical space comprising 61 monomers and identify promising candidates for high Tg fluorinated polymers. The model predicts 247 entries capable of achieving a Tg over 390 K, of which 14 are experimentally validated. This study demonstrates the potential of machine learning in material design and discovery, highlighting the effectiveness of transfer learning and ensemble modeling strategies for overcoming the challenges posed by small datasets in complex copolymer systems.
Carbohydrate‐Based Reprocessable and Healable Covalent Adaptable Biofoams
Authors: Upadhyay Chandan , Ojha Umaprasana 
Published: May 2024

AbstractPolymeric foams derived from bio‐based resources and capable of self‐healing and recycling ability are of great demand to fulfill various applications and address environmental concerns related to accumulation of plastic wastes. In this article, a set of polyester‐based covalent adaptable biofoams (CABs) synthesized from carbohydrates and other bio‐derived precursors under catalyst free conditions to offer a sustainable alternative to conventional toxic isocyanate‐based polyurethane foams is reported. The dynamic β‐keto carboxylate linkages present in these biofoams impart self‐healing ability and recyclability to these samples. These CABs display adequate tensile properties especially compressive strength (≤123 MPa) and hysteresis behavior. The CABs swiftly stress relax at 150 °C and are reprocessable under similar temperature conditions. These biofoams have displayed potential for use as attachment on solar photovoltaics to augment the output efficiency. These CABs with limited swellability in polar protic solvents and adequate mechanical resilience are suitable for other commodity applications.
Quantitative muscle magnetic resonance imaging in limb‐girdle muscular dystrophy type R1 (LGMDR1): A prospective longitudinal cohort study
Authors: Forsting Johannes , Wächter Marian , Froeling Martijn , Rohm Marlena , Güttsches Anne‐Katrin , De Lorenzo Alice , Südkamp Nicolina , Kocabas Abdulhadi , Vorgerd Matthias , Enax‐Krumova Elena , Rehmann Robert , Schlaffke Lara 
Published: May 2024

Limb‐girdle muscular dystrophy (LGMD) type R1 (LGMDR1) is the most common subtype of LGMD in Europe. Prospective longitudinal data, including clinical assessments and new biomarkers such as quantitative magnetic resonance imaging (qMRI), are needed to evaluate the natural course of the disease and therapeutic options. We evaluated eight thigh and seven leg muscles of 13 LGMDR1 patients (seven females, mean age 36.7 years, body mass index 23.9 kg/m2) and 13 healthy age‐ and gender‐matched controls in a prospective longitudinal design over 1 year. Clinical assessment included testing for muscle strength with quick motor function measure (QMFM), gait analysis and patient questionnaires (neuromuscular symptom score, activity limitation [ACTIVLIM]). MRI scans were performed on a 3‐T MRI scanner, including a Dixon‐based sequence, T2 mapping and diffusion tensor imaging. The qMRI values of fat fraction (FF), water T2 relaxation time (T2), fractional anisotropy, mean diffusivity, axial diffusivity and radial diffusivity were analysed. Within the clinical outcome measures, significant deterioration between baseline and follow‐up was found for ACTIVLIM (p = 0.029), QMFM (p = 0.012). Analysis of qMRI parameters of the patient group revealed differences between time points for both FF and T2 when analysing all muscles (FF: p < 0.001; T2: p = 0.016). The highest increase of fat replacement was found in muscles with an FF of between 10% and 50% at baseline. T2 in muscles with low‐fat replacement increased significantly. No significant differences were found for the diffusion metrics. Significant correlations between qMRI metrics and clinical assessments were found at baseline and follow‐up, while only T2 changes in thigh muscles correlated with changes in ACTIVLIM over time (ρ = −0.621, p < 0.05). Clinical assessments can show deterioration of the general condition of LGMDR1 patients. qMRI measures can give additional information about underlying pathophysiology. Further research is needed to establish qMRI outcome measures for clinical trials.
Nature connection in adulthood: The role of childhood nature experiences
Authors: Barrable Alexia , Friedman Samantha , Beloyianni Vassiliki 
Published: May 2024

Abstract

Nature connection describes our relationship with the rest of the natural world. Promoting nature connection in children and adults has been identified as a worthwhile focus for education and public health, given the positive associations between nature connection, well‐being and pro‐environmental behaviours. Prior research has looked at activities that promote an individual's connection to nature, reporting that a variety of interventions can be effective. Particular emphasis has been placed on positive childhood nature experiences due to their effects on adult nature connection. Research from varied places such as New Zealand, Australia, the USA and Brazil suggest that an individual's childhood nature experiences can play a positive role in their adult connection to nature.

This paper is the first of its kind to explore the associations between childhood nature activities, both their type and frequency, and adult nature connection in a Greek sample (n = 401). We gathered the perspectives of Greek‐speaking adults using quantitative measures in an online survey.

Our results suggest that, in line with previous research, childhood nature experiences were significantly and positively correlated with adult nature connectedness. However, contrary to previous research, analysis suggested that adult nature experiences did not mediate the relationship between childhood nature experience and adult nature connection. Age was positively correlated with less structured childhood nature experiences such that older adults were more likely to have participated in unstructured outdoor activities like flower picking and general alone time outside during childhood.

Capturing retrospective self‐reports on the frequency and type of childhood nature experiences in this Greek sample helps us understand how these experiences may predict engagement and relationships with nature in adulthood. In turn, these findings inform context‐specific recommendations for encouraging nature contact in childhood. For instance, this may have implications for nature‐based learning in Greece as well as the provision of urban green and blue spaces.

Read the free Plain Language Summary for this article on the Journal blog.
Mechanical and biodegradation analysis under various environmental conditions of the waste vetiver root fiber reinforced soy composite
Authors: Pattnaik Shruti Swaroop , Behera Diptiranjan , Jali Pallavi , Behera Ajaya Kumar 
Published: May 2024

AbstractTo address the difficulty posed by non‐biodegradable thermoplastics, scientists are focusing on solid waste management research. Waste vetiver root fibers reinforced in polymerized soy matrix biomass composites were fabricated and tested for biodegradability and sustainability in different natural decomposing conditions like seawater aging and fungal and termite attacks. This study reports and compares the dimensional changes caused by these attacks, as well as the moisture absorption of vetiver‐soy and alkali‐treated vetiver‐soy composites at different relative humidity. After‐degradation characterizations included Fourier transform infrared spectroscopy and SEM examinations, as well as weight loss, which gave additional insights into the degradation mechanism. The tensile strength of degraded samples decreased as the degradation duration increased. Mechanical properties like Izod impact strength, dynamic mechanical analysis and moisture absorption also provided insights into the structural firmness of the fabricated composite. This research contributes to a better knowledge of the bio‐deterioration process of cellulosic vetiver‐soy biocomposites under various situations, and to check their functionality in furniture and packaging industries. © 2024 Society of Chemical Industry.
Comparison of dose selection based on target engagement versus inhibition of receptor–ligand interaction for checkpoint inhibitors
Authors: Head Sarah A. , Johnson Carter , Sarkar Saheli , Matteson Andrew , Marcantonio Diana H. , Hua Fei , Burke John M. , Apgar Joshua F. , Flowers David 
Published: May 2024

AbstractImmune checkpoint inhibitors block the interaction between a receptor on one cell and its ligand on another cell, thus preventing the transduction of an immunosuppressive signal. While inhibition of the receptor–ligand interaction is key to the pharmacological activity of these drugs, it can be technically challenging to measure these intercellular interactions directly. Instead, target engagement (or receptor occupancy) is commonly measured, but may not always be an accurate predictor of receptor–ligand inhibition, and can be misleading when used to inform clinical dose projections for this class of drugs. In this study, a mathematical model explicitly representing the intercellular receptor–ligand interaction is used to compare dose prediction based on target engagement or receptor–ligand inhibition for two checkpoint inhibitors, atezolizumab and magrolimab. For atezolizumab, there is little difference between target engagement and receptor–ligand inhibition, but for magrolimab, the model predicts that receptor–ligand inhibition is significantly less than target engagement. The key variables explaining the difference between these two drugs are the relative concentrations of the target receptors and their ligands. Drug‐target affinity and receptor–ligand affinity can also have divergent effects on target engagement and inhibition. These results suggest that it is important to consider ligand–receptor inhibition in addition to target engagement and demonstrate the impact of using modeling for efficacious dose estimation.
Fatigue reliability evaluation for impellers with consideration of multi‐source uncertainties using a WOA‐XGBoost surrogate model
Authors: Qian Cheng , Li Wenjuan , Wei Shengxing , Sun Bo , Ren Yi 
Published: May 2024

AbstractWhen using Monte Carlo simulation involving repeated finite element analysis (FEA) to perform fatigue reliability evaluation for an impeller, a variety of uncertainties should be considered to ensure the comprehensiveness of fatigue predictions. These uncertainties include the aleatory uncertainty from the geometric, material and load condition, and epistemic uncertainty from the parameters of the physics‐of‐failure (PoF) model to yield fatigue prediction. However, the latter uncertainty is often ignored in fatigue reliability analysis. And the reliability assessment will become computationally unaffordable and inefficient when there are many random variables involved, as an enormous amount of FEAs are demanded. To address this problem, a Whale Optimization Algorithm‐extreme gradient boosting (WOA‐XGBoost) surrogate model is developed, based on relatively few FEA results obtained using a Latin hypercube sampling (LHS). Its strengths lie in the interpretability of the design variables and effective determination of fine‐tuned hyperparameters. A case study on an impeller is conducted considering uncertainties from 11 input variables, where an efficient XGBoost model with an R2 greater than 0.93 on test set is established using 400 samples from practical FEAs. In addition, the importance analysis indicates that elasticity modulus and density play the greatest impact on the maximum strain, showing a combined importance of 82.3%. Furthermore, the reliability assessment results under fatigue parameter derived from the Median method tend to be more conservative compared to those obtained from the Seeger method.
Chiral structures in azobenzene‐containing systems: Construction, regulation, and application
Authors: He Zixiang , Cheng Xiaoxiao , Wang Zhao , Zhang Wei 
Published: May 2024

AbstractChirality is a fundamental property in nature, which is essential for the existence and survival of living organisms. Smart responsive chiroptical materials have garnered increasing attention due to their unique structural characteristics and potential applications. Among these, azobenzene (Azo), as a typical photoresponsive chromophore, plays a crucial role in constructing and controlling chiral structures. The unique cis‐trans isomerization, liquid crystallinity, and other physicochemical properties allow for a wide range of tunability in stimuli‐responsive chiroptical materials. Herein, we review the research studies in the field of chiral/achiral Azo building blocks for multilevel chiral generation as well as chiral switching, and summarize the recent advances on the applications of the chiral Azo structures from micro to macro levels. Finally, we aim to provide an overview of the potential challenges and new research opportunities for the development of novel smart responsive chiroptical materials.
On the typical structure of graphs not containing a fixed vertex‐critical subgraph
Authors: Engelberg Oren , Samotij Wojciech , Warnke Lutz 
Published: May 2024

AbstractThis work studies the typical structure of sparse ‐free graphs, that is, graphs that do not contain a subgraph isomorphic to a given graph . Extending the seminal result of Osthus, Prömel, and Taraz that addressed the case where is an odd cycle, Balogh, Morris, Samotij, and Warnke proved that, for every , the structure of a random ‐free graph with vertices and edges undergoes a phase transition when crosses an explicit (sharp) threshold function . They conjectured that a similar threshold phenomenon occurs when is replaced by any strictly 2‐balanced, edge‐critical graph . In this paper, we resolve this conjecture. In fact, we prove that the structure of a typical ‐free graph undergoes an analogous phase transition for every in a family of vertex‐critical graphs that includes all edge‐critical graphs.
Efficient Intra‐Supramolecular Electron Transfer in Zinc Porphyrin‐Coumarin Dyads
Authors: Eldeeb Alzahraa M. , Mousa Karim , El‐Mashtoly Samir F. , El‐Khouly Mohamed E. 
Published: May 2024

AbstractWe report herein the electron transfer process of a novel supramolecular dyads composed of zinc tetraphenylporphyrin (ZnTPP) and zinc 5,15‐dinonyl‐10,20‐diphenylporphyrin (ZnDPP), as electron donors, and ethyl(4‐pyridyl) coumarin‐3‐carboxylate (EPCC), as an electron acceptor, through metal‐ligand coordination bond in dichloromethane. The optical absorption studies revealed the formation of the moderate stable supramolecular donor‐acceptor dyads. The fluorescence measurements showed a significant fluorescence quenching of the singlet‐excited state of the singlet‐excited states of ZnTPP and ZnDPP upon addition of different amounts of EPCC. Such quenching behavior could be attributed to the electron transfer from the singlet‐excited state of porphyrin to EPCC. The bimolecular quenching rates were determined to be 1.98×1012 and 7.59×1012 L mol−1 s−1 for ZnTPP‐EPCC and ZnDPP‐EPCC, respectively, respectively. The fluorescence lifetime measurements suggest fast and efficient intra‐supramolecular electron transfer from the singlet states of porphyrin derivatives to EPCC. Furthermore, the formation of the supramolecular dyads was confirmed by the Raman technique and computational studies. The finding that the examined zinc porphyrin ‐ coumarin supramolecular dyads absorb light in a wide range of UV‐visible spectrum, fast and efficient electron transfer render the examined supramolecular dyad as simple models for the reaction centers of the artificial photosynthetic systems.
Bifunctional Squaramide‐Catalyzed Asymmetric Michael/Cyclization Reactions of 3‐Hydroxychromenones with Isatylidenemalononitriles
Authors: Geng Xue‐Yang , Du Da‐Ming 
Published: May 2024

AbstractA squaramide‐catalyzed asymmetric Michael/cyclization tandem reaction between 3‐hydroxychromenones and isatylidenemalononitriles was developed. Using this strategy, a wide scope of spiro[indoline‐3,4′‐pyrano[3,2‐b]chromene] derivatives, which combined chromone, pyran, indolone in one molecule, could be obtained in moderate to excellent yields (up to 94 %) with moderate enantioselectivities (up to 95 % ee). In addition, the scaled‐up experiment also confirmed the synthetic practicality of this synthetic strategy.
Pharmacological Perspectives of 2‐alkoxy‐3‐Cyanopyridine Scaffolds: An Up‐to‐Date Review
Authors: Mahesha Priyanka , Shetty Nitinkumar S. 
Published: May 2024

AbstractThe 2‐alkoxy‐3‐cyanopyridine derivatives’ straightforward synthesis, ease of structural manipulation, and variety of intriguing biological activity continue to captivate medicinal chemists. A substantial body of research has demonstrated that these derivatives exhibit several intriguing biological characteristics, including anticancer, antibacterial, antidiabetic, antioxidant, vasorelaxant, antiviral, and anti‐inflammatory effects. Based on the basic skeleton of 2‐alkoxy‐3‐cyanopyridine, some lead compounds have been prepared with varied pharmaceutical characteristics. These served as excellent models for the development of novel medications since they showed potential in vitro and in vivo action against several cell lines that were both drug‐susceptible and drug‐resistant. To expand the use of 2‐alkoxy‐3‐cyanopyridine in biomedicine, though, a lot more efforts are essential. To combat medication resistance and boost specificity, potential hybrids that unite the 2‐alkoxy‐3‐cyanopyridine moiety with other pharmacophores are indeed required. This review offers a summary of pharmacological screening, including studies of pertinent structure‐activity connections, action mechanisms, and potential therapeutic use.
A Review of Synthetic Application of Homogeneous, Heterogenised‐Homogeneous, and Microwave‐Assisted Catalytic Carbonylation of Selected Substrates
Authors: Pant Bhawana , Prakash Deep , Dhami Devendra Singh 
Published: May 2024

AbstractCatalytic carbonylation has gained a lot of interest over the past 20 years. It produced various pharmaceuticals, agrochemicals, and intermediates that can made through this process. The carbonylation process is the most straightforward method to insert CO into any organic substrate using a simple carbonyl source, i. e., CO gas. Apart from gaseous CO, many techniques have devised for producing CO in situ using surrogates such as HCOOH, DMF, Formic acid, Phenyl Formate, Oxalic acid, and Chloroform. Several carbonylation methods, such as aminocarbonylation, alkoxycarbonylation, double carbonylation, and oxidative carbonylation, provide viable and appealing substitutes for conventional synthetic methods on a commercial or laboratory scale. Many recent studies focus on catalyst‐product separation, catalyst recoverability, and reusability in these reactions. Therefore, advancements in using different approaches, such as supported liquid phase catalysis and biphasic catalysis, to anchor homogeneous catalysts are becoming increasingly important. These carbonylation methods are easy to use, cost‐effective, and do not require ligands. They also produce excellent yields of the products necessary. Using phosphine ligands has drawbacks, including high work‐up costs, laborious work‐up techniques, and sensitivity to air and moisture. Several phosphine‐free carbonylation pathways offer affordable and straightforward ways to accomplish these changes without phosphine ligands. This review summarizes the synthetic application of homogeneous and immobilized catalysts in producing carboxylic acid derivatives and heterocycles that have medicinal properties.