bluuebunny/crossref_metadata_2025_split huggingface dataset:
Manipulating Electron‐Transfer Events in [Fe4Co4] Cubes via a Mixed‐Ligand Approach: The Impact of Elastic Frustration
Authors: Chen Zi‐Yi , Liu Qi , Cheng Yue , Deng Yi‐Fei , Liu Shihao , Wang Xin‐Yi , Zhang Yuan‐Zhu 
Published: May 2023

AbstractThe engineering of intermolecular interaction is challenging but critical for magnetically switchable molecules. Here, we prepared two cyanide‐bridged [Fe4Co4] cube complexes via the alkynyl‐ and alcohol‐functionalized trispyrazoyl capping ligands. The alkynyl‐functionalized complex 1 exhibited a thermally‐induced incomplete metal‐to‐metal electron transfer (MMET) behaviour at around 220 K, while the mixed alkynyl/alcohol‐functionalized cube of 2 showed a complete and abrupt MMET behaviour at 232 K. Remarkably, both compounds showed a long‐lived photo‐induced metastable state up to 200 K. The crystallographic study demonstrated that the incomplete transition of 1 was likely due to the possible elastic frustration originating from the competition between the anion‐propagated elastic interactions and inter‐cluster alkynyl‐alkynyl & CH‐alkynyl interactions, whereas the latter are eliminated in 2 as a result of the partial substitution by the alcohol‐functionalized ligand. Additionally, the introduction of chemically distinguishable cobalt centers within the cube unit of 2 did not lead to a two‐step but a one‐step transition, possibly because of the strong ferroelastic intramolecular interaction through the cyanide bridges.
Development of Tough Thermoplastic Elastomers by Leveraging Rigid–Flexible Supramolecular Segment Interplays
Authors: Wang Luping , Guo Longfei , Zhang Kaiqiang , Xia Yuguo , Hao Jingcheng , Wang Xu 
Published: May 2023

AbstractSupramolecular interactions facilitate the development of tough multifunctional thermoplastic elastomers. However, the fundamental principles that govern supramolecular toughening are barely understood, and the rational design to achieve the desired high toughness remains daunting. Herein, we report a simple and robust method for toughening thermoplastic elastomers by rationally tailoring hard–soft phase separation structures containing rigid and flexible supramolecular segments. The introduced functional segments with distinct structural rigidities provide mismatched supramolecular interactions to efficiently tune the energy dissipation and bear an external load. The optimal supramolecular elastomer containing aromatic amide and acylsemicarbazide moieties demonstrates a record toughness (1.2 GJ m−3), extraordinary crack tolerance (fracture energy 282.5 kJ m−2), an ultrahigh true stress at break (2.3 GPa), good elasticity, healing ability, recyclability, and impact resistance. The toughening mechanism is validated by testing various elastomers, confirming the potential for designing and developing super‐tough supramolecular materials with promising applications in aerospace and electronics.
Sandwich‐Kernelled AgCu Nanoclusters with Golden Ratio Geometry and Promising Photothermal Efficiency
Authors: Fang Liang , Fan Wentao , Bian Guoqing , Wang Runguo , You Qing , Gu Wanmiao , Xia Nan , Liao Lingwen , Li Jin , Deng Haiteng , Yan Nan , Wu Zhikun 
Published: May 2023

AbstractMetal nanoclusters have recently attracted extensive interest from the scientific community. However, unlike carbon‐based materials and metal nanocrystals, they rarely exhibit a sheet kernel structure, probably owing to the instability caused by the high exposure of metal atoms (particularly in the relatively less noble Ag or Cu nanoclusters) in such a structure. Herein, we synthesized a novel AgCu nanocluster with a sandwich‐like kernel (diameter≈0.9 nm and length≈0.25 nm) by introducing the furfuryl mercaptan ligand (FUR) and the alloying strategy. Interestingly, the kernel consists of a centered silver atom and two planar Ag10 pentacle units with completely mirrored symmetry after a rotation of 36 degrees. The two Ag10 pentacles and some extended structures show an unreported golden ratio geometry, and the two inner five‐membered rings and the centered Ag atom form an unanticipated full‐metal ferrocene‐like structure. The featured kernel structure causes the dominant radial direction transition of excitation electrons, as determined via time‐dependent density functional theory calculations, which affords the protruding absorption at 612 nm and contributes to the promising photothermal conversion efficiency of 67.6 % of the as‐obtained nanocluster, having important implications for structure‐property correlation and the development of nanocluser‐based photothermal materials.
Influences of probe shape and surface roughness on tack properties measured by the probe tack test and characterization of crosslinked polyacrylic pressure‐sensitive adhesives
Authors: Nakamura Yoshinobu , Kishimoto Risa , Nishi Hiroki , Uchimura Natsuki , Yoden Hiroyuki , Hikasa Shigeki , Iwata Hideki , Urahama Yoshiaki , Hirai Tomoyasu , Fujii Syuji 
Published: May 2023

AbstractFor a probe tack test for a pressure‐sensitive adhesive (PSA) under the conditions of light contact pressure and short contact time, probes with shapes and surface roughnesses suitable to achieve better wettability were investigated. A smooth, polished probe that became slightly convex at its center was found to be superior to flat‐ended. High surface roughness decreased tack. Debonding observations showed that fibrillation started from the probe edge and extended to the center. The fibril grew, without peeling, until the peak of the force–displacement curve was reached. After the peak, the fibril growth and peeling advanced simultaneously. The fibrillation was important to tack development. The test conditions necessary to observe the deformation behavior of PSA tape with sufficient interfacial adhesion were investigated. The system was preheated at 60°C for 1 h after the probe and PSA tape contacted each other, and was then cooled. The PSA performance of crosslinked random copolymers poly(n‐butyl acrylate‐acrylic acid) (A) and poly(2‐ethylhexyl acrylate‐acrylic acid) (B) were compared. A shoulder formed by fibrillation after the peak in the force–displacement curve was observed only for B. Copolymer B exhibited better interfacial adhesion and deformability. The preheating method was found to be useful for characterizing PSAs.
Flame‐resistant and tough polyvinyl alcohol film with ultraviolet‐absorbing capacity
Authors: Wang Chenlin , Zhang Zhihao , Ma Zhongying , Zhou Zhenzhu , Huang Junchao , Wang Yuhua 
Published: May 2023

AbstractFireproofing the polyvinyl alcohol (PVA) membrane is an essential and urgent reinforcement to ease the restriction in flame‐resistant requirements. The traditional method by the physical and heterogenous introduction of a large number of metal hydroxides, halogenated and organic compounds efficiently enhance the flame‐retardancy but severely weakens the biocompatibility, mechanical strength, and transparency of PVA membranes. In this work, two bio‐extracted compounds, phytic acid (PA) and creatine (CR) are employed to construct a fireproof, tough and transparent PVA membrane. The LOI of the PVA/PACR membrane increases from 18% to 30% and reaches a V–0 grade in UL‐94 testing. Meanwhile, the mechanical strength receives 20% reinforcement due to a chemical crosslinking between PVA, PA, and CR. Intriguingly, unsaturated chemical bonds from PA and CR endow a favorable UV‐absorbing capacity to the PVA membrane, which will benefit the anti‐aging and food freshness retaining demands in advanced packaging applications.
Body Mass Index and the Risk of Rheumatic Disease: Linear and Nonlinear Mendelian Randomization Analyses
Authors: Karlsson Torgny , Hadizadeh Fatemeh , Rask‐Andersen Mathias , Johansson Åsa , Ek Weronica E. 
Published: May 2023

ObjectiveAlthough the association between obesity and risk of rheumatic disease is well established, the precise causal relation has not been conclusively proven. Here, we estimate the causal effect of body mass index (BMI) on the risk of developing 5 different rheumatic diseases.MethodsLinear and nonlinear mendelian randomization (MR) were used to estimate the effect of BMI on risk of rheumatic disease, and sex‐specific effects were identified. Analyses were performed in 361,952 participants from the UK Biobank cohort for 5 rheumatic diseases: rheumatoid arthritis (n = 8,381 cases), osteoarthritis (n = 87,430), psoriatic arthropathy (n = 933), gout (n = 13,638), and inflammatory spondylitis (n = 4,328).ResultsUsing linear MR, we found that 1 SD increase in BMI increases the incidence rate for rheumatoid arthritis (incidence rate ratio [IRR] 1.52 [95% confidence interval (95% CI) 1.36–1.69]), osteoarthritis (IRR 1.49 [95% CI 1.43–1.55]), psoriatic arthropathy (IRR 1.80 [95% CI 1.31–2.48]), gout (IRR 1.73 [95% CI 1.56–1.92]), and inflammatory spondylitis (IRR 1.34 [95% CI 1.14–1.57]) in all individuals. BMI was found to be a stronger risk factor in women compared to men for psoriatic arthropathy (P for sex interaction = 3.3 × 10−4) and gout (P for sex interaction = 4.3 × 10−3), and the effect on osteoarthritis was stronger in premenopausal compared to postmenopausal women (P = 1.8 × 10−3). Nonlinear effects of BMI were identified for osteoarthritis and gout in men, and for gout in women. The nonlinearity for gout was also more extreme in men compared to women (P = 0.03).ConclusionHigher BMI causes an increased risk for rheumatic disease, an effect that is more pronounced in women for both gout and psoriatic arthropathy. The novel sex‐ and BMI‐specific causal effects identified here provide further insight into rheumatic disease etiology and mark an important step toward personalized medicine.
A putative adverse outcome network for neonatal mortality and lower birth weight in rodents: Applicability to per‐ and polyfluoroalkyl substances and relevance to human health
Authors: Rogers John M. , Heintz Melissa M. , Thompson Chad M. , Haws Laurie C. 
Published: May 2023

AbstractBackgroundSome per‐ and poly‐fluoroalkyl substances (PFAS) cause neonatal mortality and lower birth weight in rodents. We constructed an Adverse Outcome Pathway (AOP) network for neonatal mortality and lower birth weight in rodents, comprising three putative AOPs. We then assessed strengths of the evidence for the AOPs and applicability to PFAS. Finally, we considered the relevance of this AOP network to human health.MethodsLiterature searches targeted PFAS, peroxisome proliferator‐activated receptor (PPAR) agonists, other nuclear receptors, relevant tissues, and developmental targets. We used reviews of established biology and described results of studies with prenatal PFAS exposure that assessed birth weight and neonatal survival. Molecular initiating events (MIEs) and key events (KEs) were proposed and strengths of KE relationships (KERs), applicability to PFAS, and human relevance were assessed.ResultsNeonatal mortality has been observed in rodents following gestational exposure to most longer chain PFAS studied, often coincident with lower birth weight. In AOP 1, PPARα activation and PPARγ activation or downregulation are MIEs; placental insufficiency, fetal nutrient restriction, neonatal hepatic glycogen deficit, and hypoglycemia are KEs leading to neonatal mortality and lower birth weight. In AOP 2, constitutive androstane receptor (CAR) and pregnane X receptor (PXR) activation upregulates Phase II metabolism, lowering maternal circulating thyroid hormones. In AOP 3, disrupted pulmonary surfactant function and PPARγ downregulation cause neonatal airway collapse and mortality from respiratory failure.ConclusionsIt is likely that different components of this AOP network will apply to different PFAS, largely determined by which nuclear receptors they activate. The MIEs and KEs in this AOP network can occur in humans, but differences in PPAR structure and function, and the timeline of liver and lung development, suggest that humans may be less susceptible to this AOP network. This putative AOP network elucidates knowledge gaps and research needed to better understand the developmental toxicity of PFAS.
Predictive scaling of fiber‐based protein A capture chromatography using mechanistic modeling
Authors: Hahn Tobias , Trunzer Tatjana , Rusly Florence , Zolyomi Ryan , Shekhawat Lalita K. , Malmquist Gunnar , Hesslein Ashley , Tjandra Hendri 
Published: May 2023

AbstractProtein A affinity chromatography is an important step in the purification of monoclonal antibodies (mAbs) and mAb‐derived biotherapeutics. While the biopharma industry has extensive expertise in the operation of protein A chromatography, the mechanistic understanding of the adsorption/desorption processes is still limited, and scaling up and scaling down can be challenging because of complex mass transfer effects in bead‐based resins. In convective media, such as fiber‐based technologies, complex mass transfer effects such as film and pore diffusions do not occur which facilitates the study of the adsorption phenomena in more detail and simplifies the process scale‐up. In the present study, the experimentation with small‐scale fiber‐based protein A affinity adsorber units using different flow rates forms the basis for modeling of mAb adsorption and elution behavior. The modeling approach combines aspects of both stoichiometric and colloidal adsorption models, and an empirical part for the pH. With this type of model, it was possible to describe the experimental chromatograms on a small scale very well. An in silico scale‐up could be carried out solely with the help of system and device characterization without feedstock. The adsorption model could be transferred without adaption. Although only a limited number of runs were used for modeling, the predictions of up to 37 times larger units were accurate.
Galcanezumab for the treatment of chronic migraine and medication overuse headache: Real‐world clinical evidence in a severely impaired patient population
Authors: Guerzoni Simona , Baraldi Carlo , Castro Flavia Lo , Cainazzo Maria Michela , Pani Luca 
Published: May 2023

AbstractBackgroundGalcanezumab is a monoclonal antibody acting against the calcitonin gene‐related peptide approved for the preventive treatment of migraine. The aim of this article is to explore its effectiveness and safety of galcanezumab in chronic migraine (CM) with medication overuse‐headache (MOH).MethodsSeventy‐eight patients were consecutively enrolled at the Modena headache center and followed up for 15 months. Visits were scheduled every 3 months, and the following variables were collected: the number of migraine days per month (MDM); the painkillers taken per month (PM); the number of days per month in which the patient took, at least, one painkiller; the six‐item headache impact test; and the migraine disability assessment questionnaire (MIDAS) score. Demographic features of the analyzed sample were collected at the baseline and adverse events (AEs) were collected at every visit.ResultsAfter 12 months, galcanezumab significantly reduced the MDM, the PM, the number of days on medication, the HIT‐6 as well as the MIDAS scores (all p < .0001). The greatest amelioration was obtained in the first trimester of treatment. A higher MDM, a higher NRS score at the baseline, and a higher number of failed preventive treatments negatively predict the CM relief at the year of treatment. No serious AEs were registered and only one drop‐out was due to AE.ConclusionsGalcanezumab is effective and safe for the treatment of patients affected by CM and MOH. Patients with a higher impairment at the baseline may found less benefits with galcanezumab.
RETRACTED: Exploring antecedents for the circular economy capability of micro, small and medium enterprises: An empirical study
Authors: Baral Manish Mohan , Mukherjee Subhodeep , Singh Rajesh Kr , Chittipaka Venkataiah , Kazancoglu Yigit 
Published: May 2023

AbstractMicro, small and medium enterprises (MSMEs) play an important role in the economies of developing countries. The circular economy (CE) is considered a long‐term initiative for protecting the environment by reducing waste and greenhouse gas emissions, recycling and ending planned obsolescence. This research aims to explore antecedents for the CE capability in the context of the Indian MSMEs. The current study used the extended theory of planned behaviour and institutional theory to measure CE capabilities. Seven hypotheses are developed in this study. The survey‐based research is carried out with 296 responses from the MSMEs of different sectors in India. Hypothesis testing is done using the structural equation modelling approach. Major constructs identified for this study are green economic incentives (GEIs), social pressure (SP) and attitude. These constructs have a significant association with the CE capability of MSMEs. Environmental commitment (EC) and sustainable supply chain design (SSCD) act as mediators. Insights from this study will help the top management of MSMEs to understand antecedents for CE capability. The findings show that SP and GEIs are positively associated with EC and SSCD. It is found that EC and SSCD play a complimentary mediation role. The research findings will provide a solid foundation for understanding the importance of CE capability in MSMEs and developing strategic plans to facilitate implementing CE in these small sized firms.
Replenishable prevascularized cell encapsulation devices increase graft survival and function in the subcutaneous space
Authors: Chendke Gauree S. , Kharbikar Bhushan N. , Ashe Sudipta , Faleo Gaetano , Sneddon Julie B. , Tang Qizhi , Hebrok Matthias , Desai Tejal A. 
Published: May 2023

AbstractBeta cell replacement therapy (BCRT) for patients with type 1 diabetes (T1D) improves blood glucose regulation by replenishing the endogenous beta cells destroyed by autoimmune attack. Several limitations, including immune isolation, prevent this therapy from reaching its full potential. Cell encapsulation devices used for BCRT provide a protective physical barrier for insulin‐producing beta cells, thereby protecting transplanted cells from immune attack. However, poor device engraftment posttransplantation leads to nutrient deprivation and hypoxia, causing metabolic strain on transplanted beta cells. Prevascularization of encapsulation devices at the transplantation site can help establish a host vascular network around the implant, increasing solute transport to the encapsulated cells. Here, we present a replenishable prevascularized implantation methodology (RPVIM) that allows for the vascular integration of replenishable encapsulation devices in the subcutaneous space. Empty encapsulation devices were vascularized for 14 days, after which insulin‐producing cells were inserted without disrupting the surrounding vasculature. The RPVIM devices were compared with nonprevascularized devices (Standard Implantation Methodology [SIM]) and previously established prevascularized devices (Standard Prevascularization Implantation Methodology [SPVIM]). Results show that over 75% of RPVIM devices containing stem cell‐derived insulin‐producing beta cell clusters showed a signal after 28 days of implantation in subcutaneous space. Notably, not only was the percent of RPVIM devices showing signal significantly greater than SIM and SPVIM devices, but the intraperitoneal glucose tolerance tests and histological analyses showed that encapsulated stem‐cell derived insulin‐producing beta cell clusters retained their function in the RPVIM devices, which is crucial for the successful management of T1D.
Crowd evacuation simulation in flowing fluids
Authors: Zou Xunjin , Ye Yunqing , Zhu Zhenmin , Chen Qiang 
Published: May 2023

AbstractIn this article, we propose an integrated model for simulating the interaction between crowds and fluid particles. Our focus is on simulating evacuation motion for crowds in the face of sudden floods. Our model treats both the crowd and the water as fluid particles, which allows us to incorporate various forces such as pressure, shear, buoyancy, and active forces to drive the agents. Additionally, we have designed a minimum rotational path‐planning algorithm for agents to search for safe destinations during evacuations. To develop practical crowd evacuation strategies, we observed and studied survival techniques from whirlpools and sudden changes in water levels during floods. Our simulated evacuation results provide plausible strategies for crowds to survive dangerous floods.
Vectorizing binary image boundaries with symmetric shape detection, bisection and optimal parameterization
Authors: Zhu Zaiping , You Lihua , Zhang Jian Jun 
Published: May 2023

AbstractBinary image boundary vectorization is the process of converting raster images into vector images represented with a sequence of Bézier curves. Two main factors in reconstructing parametric curves are to approximate the underlying structure of the boundaries as much as possible while using as few curves as possible. Existing methods do not perform well when considering both of these two main factors. In this article, we mimic the process of human vectorizing image boundaries by first segmenting the boundary points into multiple segments with the corner points. For the boundary points in each segment, we adopt the bisection method to find the largest number of points, which a single curve can fit. More curves will be added if the fitting error is larger than a predefined threshold. The process is repeated until all the points in the segment are fitted, thus minimizing the number of Bézier curves. Besides, symmetric image boundaries can be detected and used to further decrease the number of curves required. Our method can also choose the optimal parameterization method case by case to further reduce the fitting error. We make a comparison with both new and classical methods and show that our method outperforms them.
Polycephalums A and B, New Anticoagulant Constituents Isolated from Clinopodium polycephalum
Authors: Tao Muke , Liu Yaxuan , Zhou Xiangmin , Yu Xinlan , Zhang Yi , Guo Li , Meng Dali 
Published: May 2023

AbstractTwo previously undescribed compounds (1 and 2) were isolated from Clinopodium polycephalum, a medicinal plant distributed in southwestern and eastern China. Their structures were elucidated using MS analyses and extensive 2D‐homo and heteronuclear NMR data interpretations. Both compounds 1 and 2 could significantly shorten APTT and PT, and their procoagulant effect was comparable to that of positive drugs. At the same time, compound 2 had certain antioxidant activity (IC50 value of 2.25±0.05 μM in ABTS assay).
Fluorenylidene‐Cyclopentadithiophene Based Asymmetric Bistricyclic Aromatic Ene Compounds: Synthesis and Substituents Effects
Authors: Xiao Beibei , Yang Yongrui , Chen Shengnan , Zou Ye , Chen Xing , Liu Kanglei , Wang Nan , Qiao Yali , Yin Xiaodong 
Published: May 2023

AbstractLow band gap materials have always been a focus of attention due to their potential applications in various fields. In this work, a series of asymmetric bistricyclic aromatic ene (BAE) compounds with fluorenylidene‐cyclopentadithiophene (FYT) skeleton were facially synthesized, which were modified with different substituents (−OMe, −SMe). The FYT core exhibit twisted C=C bond with dihedral angles around 30°, and the introduction of −SMe group can provide additional S⋅⋅⋅S interaction between molecules, which is conducive to the charge transporting. The UV‐Vis spectra, electrochemistry and photoelectron spectroscopy revealed that these compounds have relatively narrow band gaps, particularly, the −SMe modified compounds have slightly lower HOMO and Fermi energy levels than that of the −OMe modified compounds. Furthermore, PSCs devices were fabricated with the three compounds as HTMs, and FYT‐DSDPA exhibit the best performance among them, revealing the fine‐tuning band structure could influence properties of HTMs.