bluuebunny/crossref_metadata_2025 huggingface dataset:
Precise Molecular Design for Two Parent BN‐Pentacyclic Isomers Through Stitching Engineering Toward Extremely Sensitive Explosive Detection
Authors: Huang Huanan , Yao Junxiong , Xu Han , Li Jiaqi , Wang Hanbin , Xiong Cheng , Fang Binhua , Wang Yawei , Zhou Ying , Cao Xiaohua , Wang Jianguo , Tang Ben Zhong
Published: December 2022

The incorporation of BN units into polycyclic aromatic hydrocarbons (PAHs) has been ascertained to be a promising strategy for creating novel materials with unique functions and properties. However, it poses a formidable challenge to achieve precise construction of BN‐PAHs with variable skeleton module, which conversely, enhances greater understanding of the structure‐property relationship. Herein, two BN‐pentacyclic isomers (P‐BN‐BT and I‐BN‐BT) with different stitching patterns are addressed comprehensively, in which the integrated analysis reveals that the geometric structure, aromaticity, and photophysical properties indeed vary with the variational stitching models. More interestingly, further investigations show that the I‐BN‐BT with twisted molecular configuration displays a low fluorescence quantum yield, while the P‐BN‐BT with fully planar conformation exhibits high quantum yield and exceptional mechanochromic luminescent (MCL) properties. More importantly, P‐BN‐BT shows extreme sensitivity toward 2,4,6‐trinitrophenol (TNP). Visual detection of TNP is handily performed by fabrication of the test strips, which reaches ppm level under daylight. This work provides systematic insight into the effects of BN doping and highlights the importance of accurate control of the stitching patterns in conjugated materials.
Feature Space of XRD Patterns Constructed by an Autoencoder
Authors: Utimula Keishu , Yano Masao , Kimoto Hiroyuki , Hongo Kenta , Nakano Kousuke , Maezono Ryo
Published: December 2022

X‐ray diffraction (XRD) is commonly used to analyze systematic variations occurring in compounds to tune their material properties. Machine learning can be used to extract such significant systematics among a series of observed peak patterns. The feature space concept, in the context of autoencoders, can be the platform for performing such extractions, where each peak pattern is projected into a space to extract the systematics. Herein, an autoencoder is trained to learn to detect the systematics driven by atomic substitutions within a single phase without structural transitions. The feature space constructed by the trained autoencoder classifies the substitution compositions of XRD patterns satisfactorily. The compositions interpolated in the feature space are in good agreement with those of an XRD pattern projected to a point. Subsequently, the autoencoder generates a virtual XRD pattern from an interpolated point in the feature space. When the feature space is effectively optimized by enough training data, the autoencoder predicts an XRD pattern with a concentration, which is difficult to be described using the possible resolution of the supercell method of ab initio calculations.
Architecture Design and Catalytic Activity: Non‐Noble Bimetallic CoFe/fe3O4 Core–Shell Structures for CO2 Hydrogenation
Authors: Miao Wenkang , Hao Ronghui , Wang Jingzhou , Wang Zihan , Lin Wenxin , Liu Heguang , Feng Zhenjie , Lyu Yingchun , Li Qianqian , Jia Dongling , Ouyang Runhai , Cheng Jipeng , Nie Anmin , Wu Jinsong
Published: December 2022

Non‐noble metal catalysts now play a key role in promoting efficiently and economically catalytic reduction of CO2 into clean energy, which is an important strategy to ameliorate global warming and resource shortage issues. Here, a non‐noble bimetallic catalyst of CoFe/Fe3O4 nanoparticles is successfully designed with a core–shell structure that is well dispersed on the defect‐rich carbon substrate for the hydrogenation of CO2 under mild conditions. The catalysts exhibit a high CO2 conversion activity with the rate of 30% and CO selectivity of 99%, and extremely robust stability without performance decay over 90 h in the reverse water gas shift reaction process. Notably, it is found that the reversible exsolution/dissolution of cobalt in the Fe3O4 shell will lead to a dynamic and reversible deactivation/regeneration of the catalysts, accompanying by shell thickness breathing during the repeated cycles, via atomic structure study of the catalysts at different reaction stages. Combined with density functional theory calculations, the catalytic activity reversible regeneration mechanism is proposed. This work reveals the structure–property relationship for rational structure design of the advanced non‐noble metallic catalyst materials with much improved performance.
Targeting the Lysosomal Degradation of Rab22a‐NeoF1 Fusion Protein for Osteosarcoma Lung Metastasis
Authors: Zeng Cuiling , Zhong Li , Liu Wenqiang , Zhang Yu , Yu Xinhao , Wang Xin , Zhang Ruhua , Kang Tiebang , Liao Dan
Published: December 2022

Rab22a‐NeoF fusion protein has recently been reported as a promising target for osteosarcoma lung metastasis. However, how this fusion protein is regulated in cells remains unknown. Here, using multiple screenings, it is reported that Rab22a‐NeoF1 fusion protein is degraded by an E3 ligase STUB1 via the autophagy receptor NDP52‐mediated lysosome pathway, which is facilitated by PINK1 kinase. Mechanistically, STUB1 catalyzes the K63‐linked ubiquitin chains on lysine112 of Rab22a‐NeoF1, which is responsible for the binding of Rab22a‐NeoF1 to NDP52, resulting in lysosomal degradation of Rab22a‐NeoF1. PINK1 is able to phosphorylate Rab22a‐NeoF1 at serine120, which promotes ubiquitination and degradation of Rab22a‐NeoF1. Consistently, by upregulating PINK1, Sorafenib and Regorafenib can inhibit osteosarcoma lung metastasis induced by Rab22a‐NeoF1. These findings reveal that the lysosomal degradation of Rab22a‐NeoF1 fusion protein is targetable for osteosarcoma lung metastasis, proposing that Sorafenib and Regorafenib may benefit cancer patients who are positive for the RAB22A‐NeoF1 fusion gene.
Prospects of Utilizing Quantum Emitters to Control the Absorption of Non‐Noble Plasmonic Metal Nanoparticles
Authors: Steinfeld Lucinda , Cole Jared H. , Hapuarachchi Harini
Published: December 2022

Prospects of controlling the absorption of the cost‐effective plasmonic metal nanoparticles (MNPs) Cu and Al using quantum emitters (QEs) are demonstrated semi‐analytically. The resulting spectra are compared with the absorption of commonly used noble plasmonic metal nanoparticles Au and Ag under similar conditions. It is observed that Cu and Au based plasmonic nanoparticles exhibit largely similar exciton–plasmon Fano interaction signatures in addition to their similar spectral regions of operation (lower end of the visible range). Furthermore, the QE‐enhanced maximum absorption (Fano maximum) of Cu based nanohybrids are seen to approach the maximum absorption level of isolated Au MNPs, with decreasing QE‐Cu separation, increasing QE dipole element magnitude, and increasing medium permittivity, in the parameter region considered. This renders Cu based exciton–plasmon nanohybrids as more economical alternatives for Au MNPs and Au‐based nanohybrids in absorption‐based applications (such as thermoplasmonic), when stabilized in protective embedding media such as poly (methyl methacrylate) (PMMA).
Helge Willner (1947–2022)
Authors: Finze Maik , Gerken Michael
Published: December 2022

Helge Willner, ehemaliger Professor an der Bergischen Universität Wuppertal, ist am 4. September 2022 verstorben. Zahlreiche grundlegende Arbeiten auf dem Gebiet der Übergangsmetallcarbonyl‐Kationen, zu schwach koordinierenden Borat‐Anionen und zu kleinen hochreaktiven Molekülen wurden von ihm publiziert. Er wird als erstklassiger Forscher, begeisternder Lehrer und als guter Kollege und Freund in Erinnerung bleiben.
The characteristics and mechanism of hydrogen bonding assembly in linear polyurethane with multiple pendant 2‐ureido‐4[1H]‐pyrimidone units
Authors: Chen Yimei , Yang Wei , Liu Juan , Wang Yuanliang , Luo Yanfeng
Published: December 2022

2‐Ureido‐4[1H]‐pyrimidone (UPy) can form strong quadruple hydrogen bonding (H‐bonding) and is widely used to construct supramolecules. Though the H‐bonding assembly of UPy‐containing polymers has been widely reported, little attention is paid to the H‐bonding characteristics and mechanism of UPy‐containing polyurethanes. Here, by using UPy‐p‐PDLLA‐SMPU, a linear polyurethane with multiple pendant UPy units as the model polymer, the H‐bonding assembly characteristics in solution, solid film and melt are systematically investigated. It is found that the UPy units mainly exist as free monomers in DMSO, UPy dimers in CHCl3, and both free monomers and dimers in DMF. The dimerization of UPy can promote the H‐bonding of urea and urethane groups and thus the formation of hard segment aggregates. Thereby, the thermal resistance and reversibility of the H‐bonds are significantly enhanced in both UPy‐p‐PDLLA‐SMPU film and melt. UPy‐p‐PDLLA‐SMPU can transition from a rubber state (70°C–85°C) to a viscous flow state (≥120°C), presenting the characteristics of both chemically crosslinked and linear polyurethanes. This work provides a clear picture on the H‐bonding assembly of UPy units together with urea and urethane groups in UPy‐p‐PDLLA‐SMPU. The obtained assembly characteristics and mechanism are beneficial for the design and processing of UPy‐based physically crosslinked polyurethanes.
Preparation and characterization of hydrogel from deacetylated xanthan gum produced by Xanthomonas arboricola pv pruni 106
Authors: de Oliveira Molon Bruna , de Oliveira Molon Bianca , Gonçalves Janaina Oliveira , Ribeiro Eduardo Silveira , Diaz Patrícia Silva
Published: December 2022

Xanthan gum is a water‐soluble polysaccharide obtained by fermentation of the genus Xanthomonas with several properties, such as low‐cost, biodegradability, biocompatibility and non‐toxicity. However, an important limitation of xanthan gum‐based biomaterials is the high swelling degree in solvent and the mechanical weakness, which results in biomaterial disintegration. For this reason, the aim of this work was to develop a hydrogel with reduced swelling degree. The xanthan gum produced by X. arboricola pv pruni 106 achieved a volumetric yield of 10.78 ± 0.27 g L−1. The content of acetyl group was relatively low, around 1.33%, which the deacetylation process reduced its level to 0.8%. The hydrogel was produced using deacetylated xanthan gum and glutaraldehyde as crosslinker. The xanthan gum‐based hydrogel has shown lower swelling degree and higher apparent viscosity, overcoming the initial drawbacks of the xanthan gum in its nature form. Overall, the xanthan gum‐based hydrogel has remained stable during the whole storage conditions.
Omnivorous Notoxus trinotatus Pic (Coleoptera: Anthicidae) is a newly recognized vector of northern leaf blight in maize
Authors: Feng Lichao , Du Zhiqi , Zhang Shuang , Zhang Shaoqing , Meng Qingfan , Tajovský Karel
Published: December 2022

The adaptations of omnivorous insects to food are manifested in a multifaceted manner, and the availability of food resources directly determines insect feeding tendencies, which contribute to a complex insect‐food relationship and impact insect functionality in the environment. Stable isotope analysis was applied to test the feeding preference and further define the functional role of omnivorous beetles in cropland. Our results confirmed that as an omnivorous beetle, the fungivorous nature of Notoxus trinotatus accounted for a prominent proportion food selection at the adult stage, and more importantly, this dietary feature contributed to the dispersal of the northern corn leaf blight in maize (NLB) during the feeding trials. In addition to the preference for fungi, water supplementation was an essential element extending adult longevity, which directly prolonged the contact time of adults with pathogenic fungi in agricultural fields. Consistent with the herbivorous characteristics of beetles, before the emergence of NLB fungal pathogens, corn tissues served as the main food, which provided the beetles with more opportunities to transmit fungal pathogen propagules. We conclude that the role of N. trinotatus in carrying NLB pathogen is due to its feeding on this plant mycopathogen, and an increased abundance of beetles carrying the pathogen may increase the rate of NLB disease infestation. More focus should be concentrated on the functions of fungivorous beetles, not only as pathogen‐transmitting pests, but also as an element among the balanced biotic factors in farmland.
Two‐Dimensional Materials Applied in Membranes of Redox Flow Battery
Authors: He Murong , Guan Minyuan , Zhan Ruifeng , Zhou Kaiyun , Fu Hu , Wang Xinan , Zhong Fangfang , Ding Mei , Jia Chuankun
Published: December 2022

Redox flow batteries (RFBs) are one of the most promising techniques to store and convert green and renewable energy, benefiting from their advantages of high safety, flexible design and long lifespan. Membranes with fast and selective ions transport are required for the advances of RFBs. Remarkably, two‐dimensional (2D) materials with high mechanical and chemical stability, strict size exclusion and abundantly modifiable functional groups, have attracted extensive attentions in the applications of energy fields. Herein, the improvements and perspectives of 2D materials working for ionic transportation and sieving in RFBs membranes are presented. The characteristics of various materials and their advantages and disadvantages in the applications of RFBs membranes particularly are focused. This review is expected to provide a guidance for the design of membranes based on 2D materials for RFBs.
H∞$$ {H}_{\infty } $$ constraint Pareto optimal control for discrete‐time Markov jump linear stochastic systems in finite horizon
Authors: Jiang Xiushan , Cui Kai , Zhao Dongya
Published: December 2022

This paper mainly focuses on discrete‐time Markov jump linear stochastic systems (DMJLSSs) with external disturbances and multiplicative noise. Due to the multi‐player in the systems and multi‐objective cost function, the strategy design for these systems is more difficult than the traditional Markov jump stochastic systems. We combine
theory with Pareto control and use the weighted sum method of the objective functional of each player to solve the problem of Pareto cooperative game. Four coupled difference matrix‐valued recursion equations (CDMREs) are derived by stochastic bounded real lemma (SBRL). Then, a sufficient and necessary condition for the existence of the Pareto optimal strategy is obtained, and the Pareto solution for every controller is derived under this strategy. A simulation example is given to verify the correctness of the theory.
Performance improvement of aircraft pitch angle control using a new reduced order fractionalized PID controller
Authors: Idir A. , Bensafia Y. , Khettab K. , Canale L.
Published: December 2022

In this paper, a new optimal reduced order fractionalized PID (ROFPID) controller based on the Harris Hawks Optimization Algorithm (HHOA) is proposed for aircraft pitch angle control. Statistical tests, analysis of the index of performance, and disturbance rejection, as well as transient and frequency responses, were all used to validate the effectiveness of the proposed approach. The performance of the proposed HHOA‐ROFPID and HHOA‐ROFPID controllers with Oustaloup and Matsuda approximations was then compared not only to the PID controller tuned by the original HHO algorithm but also to other controllers tuned by cutting‐edge meta‐heuristic algorithms such as the atom search optimization algorithm (ASOA), Salp Swarm Algorithm (SSA), sine‐cosine algorithm (SCA), and Grey wolf optimization algorithm (GOA). Simulation results show that the proposed controller with the Matsuda approximation provides better and more robust performance compared to the proposed controller with the Oustaloup approximation and other existing controllers in terms of percentage overshoot, settling time, rise time, and disturbance rejection.
Counting states: A combinatorial analysis of SQM fragmentation
Authors: Bernardo Antonio L. C. , Paulucci Laura , de Sá Lucas M. , Horvath Jorge E.
Published: December 2022

The Strange Quark Matter (SQM) hypothesis states that at extreme pressure and density conditions, a new ground state of matter would arise, in which half of the down quarks become strange quarks. If true, it would mean that at least the core of neutron stars is made of SQM. In this hypothesis, SQM would be released in the interstellar medium when two of these objects merge. It is estimated that of SQM would be released this way. This matter will undergo a sequence of processes that should result in a fraction of the released SQM becoming heavy nuclei through the r‐process. In this work, we are interested in characterizing the fragmentation of SQM, with the novelty of keeping track of the quark configuration of the fragmented matter. This is accomplished by developing a methodology to estimate the energy of each fragment as the sum of its constituent quarks, the Coulomb interaction among the quarks and fragments' momenta.
Filling the mass gap between neutron star and black hole masses
Authors: Horvath Jorge E. , Bernardo Antônio L. C. , Bachega Riis R. A. , de Sá Lucas M. , Rocha Livia S. , Moraes Pedro H. R. S.
Published: December 2022

The lack of objects between 2 and 5 M⊙ in the joint mass distribution of compact objects has been termed “mass gap” and attributed to the characteristics of the supernova mechanism at their birth. However, recent observations show that a number of candidates reported to lie inside the “gap” may fill it, and the paucity may be the result of small number statistics. We quantify in this work the individual candidates and evaluate the joint probability of a mass gap. Our results show that a mass gap is not present, to a very high confidence level. It remains to be seen if a relative paucity of objects ensues and how this population can be related to the formation processes, which may include neutron star mergers, collapse of a neutron star to a black hole and others.
High expression of caspase‐8 as a predictive factor of poor prognosis in patients with esophageal cancer
Authors: Chai Jian , Lei Yongqiang , Xiang Xindong , Ye Jing , Zhao Hang , Yi Lili
Published: December 2022

Background

Esophageal carcinoma (ESCA) is considered to be one of the most common gastrointestinal cancers. Caspase‐8 (CASP8) is a key protein of cross‐talk signaling in a variety of cancers. However, the role of CASP8 expression in the prognosis of patients with ESCA has remained unexplored. Hence, it is needed to explore the clinical significance of CASP8 expression in ESCA.

Methods

The expression and prognosis of CASP8 were investigated in ESCA using the UALCAN, GEDS, TIMER, and OncoLnc databases. The CASP8 genetic variations in ESCA were assessed using the cBioPortal database. The correlation between CASP8 expression and tumor immune invasion and immune cell surface indicators was examined using the TIMER and TISIDTISIDB datasets. Meanwhile, the abundance of the immunological cells in the tumor and healthy tissues was assessed by the CIBERSORT method. Next, information on the co‐expressed genes of the differentially expressed genes (DEGs) in ESCA‐tumor and ESCA‐healthy tissues was obtained using the cBioPortal, UALCAN, and Coexpedia databases. Subsequently, the PPI network was constructed and the GO and KEGG pathways were analyzed using the SIRING database. Finally, CASP8 mRNA and protein expression in the ESCA tissues and matched adjacent healthy tissues were analyzed using qRT‐PCR, immune‐blotting, and immunohistochemistry. Additionally, the relationship between clinicopathological features and CASP8 expression was assessed.

Results

ESCA tissues had higher levels of CASP8 mRNA and protein expression compared to healthy tissues. patients with an elevated level of CASP8 expression had poor overall survival (OS). CASP8 expression was significantly correlated with the degree of differentiation (P = 0.004) and lymph node metastasis (P = 0.044). There were diverse patterns of association between immunological cell surface biomarkers and CASP8 expression.

Conclusion

ESCA showed significant levels of CASP8 expression which may serve as a prognostic biomarker correlated to immune infiltrates in ESCA.
A comparative study of diagnostic accuracy in 3026 pleural biopsies and matched pleural effusion cytology with clinical correlation: A methodological issue
Authors: Zhang Wen‐Li , Fang Xiang , Qiu Jian‐Qing , Cui Tao
Published: December 2022

Aim

After reading the article by Ivan K. Poon et al. Certain issues regarding the methodology must be addressed.

Result

First, it was not sufficient using only sensitivity and specificity. Second, we think the receiver operator characteristic curve (ROC) as well as the index of area under curve (AUC) could better be demonstrated in this, it was not sufficient using only sensitivity and specificity. Second, we think the receiver operator characteristic curve (ROC) as well as the index of area under curve (AUC) could better be demonstrated in this article for a more comprehensive understanding of this diagnostic test accuracy when comparing different tests.

Conclusion

With using more comprehensive indexes including Youden's index, LR and AUC, the conclusions of Ivan K. Poon and his colleagues would be sodified.
ADReFV: Face video dataset based on human‐computer interaction for Alzheimer's disease recognition
Authors: Xu Tao , Wang Xinheng , Lun Xie , Pan Hang , Wang Zhiliang
Published: December 2022

With the global aging problem becoming more and more serious, the initial screening for Alzheimer's disease (AD) will become increasingly important. We understand that facial expressions are related to the severity of dementia, but there is no face‐related data in the existing Alzheimer's dataset. This article attempts to establish a facial video‐based AD recognition dataset through a human‐computer interaction method. This interactive task was designed for AD in attention, execution, visual space ability, facial apraxia, and facial changes in task success and failure. Using this task as the collection method, the final dataset includes 102 faces video data, specific task scores, and emotional self‐evaluation. For baseline evaluation, the improved local binary pattern on three orthogonal planes and RF were employed respectively for feature extraction and classification with the 5‐fold cross‐validation method. The best performance was 76.00% for 3‐class classification. In addition, a frame attention network based on fine‐grained local region localization was proposed, which improved the accuracy of cognitive classification to 84.45%. Finally, the analysis was conducted for the association of expressions with cognition and emotion in the AD dataset. This study aims to solve the current lack of standards for AD in the field of facial recognition and contribute to future research and clinical applications.
Site‐Selective Unnatural Amino Acid Incorporation at Single or Multiple Positions to Control Sugar‐Protein Connectivity in Glycoconjugate Vaccine Candidates
Authors: Violo Typhaine , Lambert Annie , Pillot Aline , Fanuel Mathieu , Mac‐Béar Jessica , Broussard Cédric , Grandjean Cyrille , Camberlein Emilie
Published: December 2022

In cellulo site‐specific unnatural amino acid incorporation based on amber stop codon reassignment is a powerful tool to modify proteins at defined positions. This technique is herein applied to the selective functionalization of the Pneumococcal surface adhesin A protein at three distinct positions. Nϵ‐propargyloxycarbonyl‐l‐lysine residues were incorporated and their alkyne groups reacted using click‐chemistry with a synthetic azido‐functionalized tetrasaccharide representative of one repeat unit of the Streptococcus pneumoniae serotype 14 capsular polysaccharide. Anti‐PsaA antibody response induced in mice by the trivalent glycoconjugate was determined in comparison with corresponding monovalent and randomly functionalized conjugates. Our results suggest that controlled was superior to random conjugation for preserving antigenicity. In definitive, the reported strategy offers a unique opportunity to study the impact of carbohydrate antigen‐carrier protein connectivity on immunogenicity.
Diastereoselective Synthesis oftrans‐anti‐Hydrophenanthrenes via Ti‐mediated Radical Cyclization and Total Synthesis of Kamebanin
Authors: Suzuki Takahiro , Ikeda Wataru , Kanno Ayaka , Ikeuchi Kazutada , Tanino Keiji
Published: December 2022

Ent‐kaurenes consist of an ABC‐ring based on atrans‐anti‐hydrophenanthrene skeleton and a D ring with an exomethylene. Highly oxygen‐functionalizedent‐kauren‐15‐ones have promising antiinflammatory pharmacological activity. In this study, we developed a novel diastereoselective synthesis oftrans‐anti‐hydrophenanthrenes via a Ti‐mediated reductive radical cyclization. We also demonstrated the applicability of this method by developing the first total synthesis of (±)‐kamebanin (longest linear sequence; 17 steps, overall yield; 6.5 %). Furthermore, this synthesis provided a formal semi‐pinacol rearrangement for the construction of the quaternary carbon at C8 and a novel Thorpe‐Ziegler‐type reaction for the construction of the D‐ring.
Trace Explosive Detection Based on Photonic Crystal Amplified Fluorescence
Authors: Chen Xiaodong , Zhang Xiujuan , Wang Hui , Zhang Lianbin , Zhu Jintao
Published: December 2022

With increasing demand for public security and environmental protection, it is highly desirable to develop strategies to identify trace explosives (e. g., 2,4,6‐trinitrotoluene (TNT)). Herein, we report novel photonic crystal (PC)‐based sensor chips for trace TNT detection by using amplification effect of PCs on fluorescence (FL) signals. The sensor chips are constructed by integrating silica nanoparticles (NPs) modified with (3‐aminopropyl)triethoxysilane (APTES) and fluorescein isothiocyanate isomer (FITC) and PC substrates. The amino groups on FITC‐APTES‐silica NPs can specifically bind with TNT molecules to form Meisenheimer complexes and strongly quench the FL signal of neighboring fluorophores FITC through Förster resonance energy transfer. PCs with matched PBG can amplify the FL signal of FITC‐APTES‐silica NPs about 24.4‐fold and significantly improve sensitivity and resolution of trace TNT detection with the limit of detection of 0.23 nM. The PC‐based sensor chips are stable, sensitive, and reliable TNT sensing platforms, showing great potential in homeland safety and environmental protection.
Cooperative Nitrile Coordination Using Nickel and a Boron‐Containing Secondary Coordination Sphere**
Authors: Clapson Marissa L. , Sharma Harvey , Zurakowski Joseph A. , Drover Marcus W.
Published: December 2022

Metal‐ligand cooperation has emerged as a versatile tool for substrate activation in chemical reactivity. Herein, we provide the synthesis and characterization of a monoboranyl‐containing analogue of the ubiquitous bulky diphosphine ligand, 1,2‐bis(di‐tert‐butylphosphino)ethane, whose reactivity has been examined using nickel. Together, the pairing of nickel and boron provides a platform that allows for the cooperative coordination of organonitriles, giving unusual examples of intermolecularly bound dinickelacycles.
Mathematical modelling of enzymatically cross‐linked polymer–phenol conjugates using deterministic and stochastic methods
Authors: Karageorgos Filippos F. , Vasileiadou Athina C. , Kiparissides Costas
Published: December 2022

In this study, two different modelling approaches, namely, a deterministic and a stochastic one, are developed to model the enzymatic cross‐linking of polymer–phenol conjugates. A comprehensive kinetic mechanism is postulated to describe the elementary reactions in the cross‐linking of polymer–phenol chains in the presence of the horseradish peroxidase (HRP)–H2O2 initiation system. In the first approach, a moments‐based model is derived to account for the conservation of all molecular species and leading moments of the number chain length distribution (NCLD) in the reactive system. In the second approach, a stochastic Monte Carlo kinetic model is formulated to follow the time evolution of a sample of cross‐linkable polymer chains and calculate the weight chain length distribution (WCLD). From the numerical solutions of both models, the dynamic evolution of the concentrations of all the reactive species, the gelation onset time, the sol and gel mass fractions as well as the number and weight average molecular weights of the cross‐linkable polymer chains are calculated. The two derived models are validated using experimental kinetic measurements on the enzymatic cross‐linking of tyramine‐modified hyaluronic acid and carboxymethyl‐chitin. It is shown that both models can accurately predict the gelation onset time of the two cross‐linkable systems over a wide range of variations in HRP and H2O2 concentrations. Finally, the MC model predictions on the weight average number of polymer chains in the cross‐linked molecules are compared to Flory's analytical solution on the tetrafunctional cross‐linking of polymer chains of uniform length.
Review and Perspective of Tailorable Metal‐Organic Framework for Enhancing Microwave Absorption
Authors: Miao Peng , Chen Juan , Chen Jianxin , Kong Jie , Chen Kai‐Jie
Published: December 2022

Comprehensive Summary

Metal‐organic frameworks (MOFs) and their pyrolytic derivates, displaying diverse chemical compositions and microstructures, provide the infinite potential for preparing high‐performance microwave absorption materials (MAMs) and have attracted extensive attention. In this review, we systematically reviewed the recent progress of MOF‐based MAMs, including three types of MOF‐based MAMs (MOF‐derived metal/carbon nanocomposites, MOF‐based hybridization materials and conductive MOF). Besides that, the microwave absorption properties and their related physical and chemical appearance were also analyzed. On behalf of synergistic effects between microstructures, dielectric components and magnetic response, the MOF‐based MAMs show excellent microwave absorption performance, which is superior to that of traditional single metal, metal alloy and pure carbon‐based MAMs. Furthermore, the novel conductive MOF with tunable electrical conductivity shows great potential in MAMs due to the fact that it can dramatically simplify the synthesis process.
Establishment of a 3D co‐culture model to investigate the role of primary fibroblasts in ductal carcinoma in situ of the breast
Authors: Sourouni Marina , Opitz Carl , Radke Isabel , Kiesel Ludwig , Tio Joke , Götte Martin , von Wahlde Marie‐Kristin
Published: December 2022

Background

Ductal carcinoma in situ (DCIS) is a precursor form of breast cancer. 13%–50% of these lesions will progress to invasive breast cancer, but the individual progression risk cannot be estimated. Therefore, all patients receive the same therapy, resulting in potential overtreatment of a large proportion of patients.

Aims

The role of the tumor microenvironment (TME) and especially of fibroblasts appears to be critical in DCIS development and a better understanding of their role may aid individualized treatment.

Methods and results

Primary fibroblasts isolated from benign or malignant punch biopsies of the breast and MCF10DCIS.com cells were seeded in a 3D cell culture system. The fibroblasts were cultured in a type I collagen layer beneath a Matrigel layer with MCF10DCIS.com cells. Dye‐quenched (DQ) fluorescent collagen I and IV were used in collagen and Matrigel layer respectively to demonstrate proteolysis. Confocal microscopy was performed on day 2, 7, and 14 to reveal morphological changes, which could indicate the transition to an invasive phenotype.

MCF10DCIS.com cells form smooth, round spheroids in co‐culture with non‐cancer associated fibroblasts (NAFs). Spheroids in co‐culture with tumor‐associated fibroblasts (TAFs) appear irregularly shaped and with an uneven surface; similar to spheroids formed from invasive cells. Therefore, these morphological changes represent the progression of an in situ to an invasive phenotype. In addition, TAFs show a higher proteolytic activity compared to NAFs. The distance between DCIS cells and fibroblasts decreases over time.

Conclusion

The TAFs seem to play an important role in the progression of DCIS to invasive breast cancer. The better characterization of the TME could lead to the identification of DCIS lesions with high or low risk of progression. This could enable personalized oncological therapy, prevention of overtreatment and individualized hormone replacement therapy after DCIS.
Temporal intensity modeling of sub‐events in microblogs
Authors: Vijayakumar Angel Petricia , Rajam V. Mary Anita
Published: December 2022

Social media has evolved into a conventional source of obtaining and tracking news events in the digital world. Most news events constitute a flow of sub‐events, that are distinct and independent events, related to the same base news event. These sub‐events have the potential to alter the course of the news event and also the emotional responses toward the news event entirely. Discovering the intensity of user attention toward sub‐events at set points of time, aids in modeling the evolution of sub‐events and consecutively, the news event as a whole. This work proposes two methodologies for day‐to‐day temporal analysis of sub‐events: a top‐down approach based on the significance of hashtags and a bottom‐up approach based on the combined intensity of components such as hashtags and tweet content. In comparison, the approach based on the combined intensity of components proves very promising in representing the temporal intensity of sub‐events.
Parkinson's disease detection using sea lion shuffled shepherd optimization assisted deep maxout network
Authors: Ramaiyar Sundaram Mohana , Swamidason Iwin Thanakumar Joseph , Sarveshwaran Velliangiri
Published: December 2022

When compared to a cloud‐based application, fog computing allows the doctor to make better decisions in an emergency and also helps secure personal data with less latency. Parkinson's disease (PD) is a kind of brain illness, which causes stiffness, shaking, trouble in walking, talking, and so on. There is various detection techniques have been invented by researchers previously, but less accuracy is a major drawback. The main purpose of this research is the effective PD detection by the progression of optimized deep maxout network (DMN), namely, sea lion shuffled shepherd optimization (SLnSSOA)‐based DMN. Here, the developed method involves fog nodes, blockchain (BC), cloud, medical analyzer, and so on. The input data, which comes from the cloud is sent to the preprocessing phase, where data normalization is used to process it. Additionally, SLnSSOA, a combination of the sea lion optimization algorithm (SLnO) and the shuffled shepherd optimization (SSOA), is used to classify diseases using DMN, where the parameters are trained using SLnSSOA. Moreover, this technique provides an improved classification outcome. The developed method attains maximum testing accuracy of 0.908, sensitivity of 0.930, and specificity of 0.875.
Clumped isotope analysis of zoned calcite cement, Carboniferous, Isle of Man
Authors: Dickson John Anthony Dawson , Hodell David A. , Swart Peter K. , Lu Chaojin , Mleneck‐Vautravers Maryline J. , Rolfe James E.
Published: December 2022

Sequential analyses of δ13C, δ18O and Δ47 values of calcite and dolomite deposited in millimetre‐sized cavities are reported from the Ronaldsway Member packstones, Isle of Man. The Ronaldsway brachiopods have δ13C values of ca +2.3‰ and δ18O values of ca −7.2‰; carbon is like predicted Carboniferous values, while oxygen values are more negative. The brachiopods show preserved microstructure but have marginal alteration and a streaky cathodoluminescence pattern. Crinoid ossicles have δ13C values of ca +2.3‰ and one with a δ18O value of ca −3.1‰, compatible with Carboniferous marine precipitates; three samples have δ18O values of ca −6.5‰ and are 18O‐depleted. Calcite stages 1 and 2 have δ13C values ca +3.2‰ and δ18O values ca −2.5‰, compatible with Carboniferous sea water. Stage 1 and 2 have non‐luminescent to orange CL zones. Stage 1 and early stage 2 contain red luminescent dolomite micro crystals generated during Mg calcite stabilisation. The Δ47 values for stage 1 and 2 cements indicate temperatures of 86 and 105°C that occurred after the stabilisation of Mg calcite. Stage 3–8 zoned cements preserve their original growth surfaces and their δ13C and δ18O values suggest precipitation during burial and exhumation. The Δ47 values of the brachiopods and crinoids indicate temperatures between 85 and 140°C indicating they were either recrystallised at high temperatures or affected by solid state reordering. To evaluate these alternatives two quantitative models, water–rock reaction and reordering models are performed. The allochems and cements are progressively altered by porewater towards the fluid‐buffered behaviour. The quantitative evaluation of calcite and dolomite solid‐state reordering suggests the elevated clumped isotopic temperatures are produced by interaction with hydrothermal fluids. This study improves understanding by applying previously untried techniques; further Δ47 data and quantifying elemental variations would help further interpretation but the poorly documented post‐depositional history is a drawback.
Differences in initial abundances reveal divergent dynamic structures in Gause's predator–prey experiments
Authors: Mühlbauer Lina Kaya , Harpole William Stanley , Clark Adam Thomas
Published: December 2022

Improved understanding of complex dynamics has revealed insights across many facets of ecology, and has enabled improved forecasts and management of future ecosystem states. However, an enduring challenge in forecasting complex dynamics remains the differentiation between complexity and stochasticity, that is, to determine whether declines in predictability are caused by stochasticity, nonlinearity, or chaos. Here, we show how to quantify the relative contributions of these factors to prediction error using Georgii Gause's iconic predator–prey microcosm experiments, which, critically, include experimental replicates that differ from one another only in initial abundances. We show that these differences in initial abundances interact with stochasticity, nonlinearity, and chaos in unique ways, allowing us to identify the impacts of these factors on prediction error. Our results suggest that jointly analyzing replicate time series across multiple, distinct starting points may be necessary for understanding and predicting the wide range of potential dynamic types in complex ecological systems.
Evolution of Graphene Supported RuN (N=1–4) Clusters in CO Atmosphere: A First‐Principles Investigation
Authors: Wu Yong , Guo Huimin , Liu Xin , Meng Changgong
Published: December 2022

We investigated the evolution of Ru clusters containing 1–4 atoms supported on graphene in CO atmosphere with extensive first principle‐based calculations. Exothermic CO adsorption induces gradual structure reorganization and change of the Ru−Ru, Ru‐graphene, and Ru‐CO interactions within these Ru carbonyls. The upper limits of CO on a surface of Ru cluster are 3, 6, 10 and 12 for Ru1, Ru2, Ru3 and Ru4, respectively. The further CO adsorption enhances steric hindrance at the Ru‐graphene interface that finally leads to release of undercoordinated Ru carbonyls into gas phase. Competing with the CO adsorption and sintering of Ru species for better thermostability, disintegration of multinuclear surface Ru carbonyls to atomically dispersed Ru species on graphene is still feasible. The current findings bring more insights into the evolution and interconversion of Ru carbonyls in a CO atmosphere and may help to understand the superior performance of heterogeneous transition metal catalysts in operation conditions.
Sleep architecture in drug‐naïve adult patients with epilepsy: Comparison between focal and generalized epilepsy
Authors: Calvello Carmen , Fernandes Mariana , Lupo Clementina , Maramieri Elena , Placidi Fabio , Izzi Francesca , Castelli Alessandro , Pagano Andrea , Mercuri Nicola Biagio , Liguori Claudio
Published: December 2022

Objective

Sleep impairment is one of the most common comorbidities affecting people with epilepsy (PWE). The bidirectional relation between epilepsy and sleep has been widely established. Several studies investigated subjective sleep quality and daytime vigilance in PWE, highlighting frequent complaints of sleep fragmentation, difficulties in falling asleep, and daytime sleepiness. The present study aimed to evaluate sleep structure in drug‐naive PWE, distributed on the basis of epilepsy type, and compared with controls.

Methods

This observational study included adult patients newly diagnosed with epilepsy and drug‐naive as well as a control group of healthy subjects. All PWE and controls underwent a dynamic 24‐h EEG with signals for sleep recording to evaluate sleep architecture, structure, continuity, and fragmentation.

Results

Twenty‐four PWE were included and distributed in two groups based on epilepsy type. Eleven patients were included in the generalized epilepsy group (63.6% male; 34.91 ± 9.80 years) and 13 patients in the focal epilepsy group (53.8% male; 38.69 ± 12.74 years). The control group included 16 subjects (56.3% male; 32.75 ± 12.19 years). Patients with generalized or focal epilepsy had a significantly lower sleep efficiency than controls. Moreover, both patient groups presented the alteration of markers of sleep fragmentation and loss of continuity, with higher indices of sleep stage transitions and arousal. Finally, the two patient groups presented less REM sleep than controls.

Significance

This study highlighted the alteration of sleep quality, continuity, and stability in both patients with focal or generalized epilepsy compared with controls, also in the absence of ictal events. This sleep impairment resulted in the reduction of REM sleep. Therefore, these findings may be explained by the increase in awakenings and sleep stage shifts, which may be attributed to both sleep networks impairment and neurotransmission dysfunction in PWE, and also possibly triggered by paroxysmal interictal abnormalities.
Microbial peroxide‐producing cell coupled in‐situ enzymatic depolymerization for lignin biorefinery
Authors: Mukhopadhyay Dhruva , Sharma Rakesh Kumar , Gupta Pratima
Published: December 2022

Lignin is one of the most versatile and complex macromolecules, which can be converted to value‐added products such as p‐coumaric acid and vanillin upon depolymerization. The current work explored oxidative lignin depolymerization in a microbial peroxide‐producing cell containing manganese peroxidase enzymes. A double‐chambered microbial peroxide‐producing cell was constructed containing the immobilized manganese peroxidase on alginate beads in the cathode chamber, while the anodic chamber contained wastewater. This setup was run for 8 days after the addition of lignin in the catholyte. The voltage measured in the circuit was 0.491 V while the current and power densities were 223 µA/cm2 and 110 µW/cm2, respectively on the 8th day of the experiment. The maximum H2O2 concentration observed was 1.5 mM on the 6th day. Depolymerization of lignin was confirmed by the change in the significant peaks at 280 nm of the ultraviolet‐visible spectrum. A change in the signature regions of β‐β linkages and β‐O‐4 linkages in the Fourier‐transform infrared spectrum was also observed. Liquid chromatography–quadrupole time of flight–mass spectrometry analysis revealed the presence of compounds including isoeugenol, acetovanillone, methacrylic acid, phenamacril, diofenolan, and jasmolin identified as the product of lignin depolymerization.
Fluorocyclisation of Oximes to Isoxazolines Through I(I)/I(III) Catalysis
Authors: Neufeld Jessica , Daniliuc Constantin G. , Gilmour Ryan
Published: December 2022

A regioselective fluorocyclisation of β,γ‐unsaturated oximes through I(I)/I(III) catalysis is disclosed to generate 5‐fluoromethylated isoxazolines. The transformation leverages p‐iodotoluene as an inexpensive catalyst, Selectfluor® as the terminal oxidant and an amine⋅HF complex (1 : 7.5) as both the fluoride and Brønsted acid source. The λ3‐iodane p‐TolIF2, which is generated in situ, engages the pendant alkene of the substrate to facilitate a cyclisation/fluorination sequence. A range of 5‐fluoromethyl isoxazolines can be generated using this method, including aliphatic and aromatic systems (up to 56 % yield). Single crystal X‐ray analysis of a representative example reveals a conformation that is consistent with the stereoelectronic gauche effect between the exocyclic C(sp3)−F bond and the C(sp3)−O of the isoxazoline (ϕOCCF=−62.0°).
Dysfunctions of innate and adaptive immune tumor microenvironment in Waldenström macroglobulinemia
Authors: Cholujova Danka , Beke Gabor , Hunter Zachary R. , Hideshima Teru , Flores Ludmila , Zeleznikova Tatiana , Harrachova Denisa , Klucar Lubos , Leiba Merav , Drgona Lubos , Treon Steven P. , Kastritis Efstathios , Dorfman David M. , Anderson Kenneth C. , Jakubikova Jana
Published: December 2022

Waldenström macroglobulinemia (WM) is a rare subtype of non‐Hodgkin lymphoma characterized by malignant lymphoplasmacytic cells in the bone marrow (BM). To dissect the pathophysiology of WM, we evaluated clonal cells by mapping of B cell lymphomagenesis with adaptive and innate immune tumor microenvironment (TME) in the BM of WM patients using mass cytometry (CyTOF). In‐depth immunophenotypic profiling of WM cells exhibited profound expansion of clonal cells in both unswitched and switched memory B cells and also plasma cells with aberrant expression variations. WM B lymphomagenesis was associated with reduction of most B cell precursors assessed with the same clonally restricted light chain and phenotypic changes. The immune TME was infiltrated by mature monocytes, neutrophils and adaptive T cells, preferentially subsets of effector T helper, effector CTL and effector memory CTL cells that were associated with superior overall survival (OS), in contrast to progenitors of T cells and myeloid/monocytic lineage subsets that were suppressed in WM cohort. Moreover, decrease in immature B and NKT cells was related to worse OS in WM patients. Innate and adaptive immune subsets of WM TME were modulated by immune checkpoints, including PD‐1/PD‐L1&PD‐L2, TIGIT/PVR, CD137/CD137‐L, CTLA‐4, BTLA and KIR expression. The response of ibrutinib treatment to the reduction of clonal memory B cell was associated with high levels of immature B cells and effector memory CTL cells. Our study demonstrates that CyTOF technology is a powerful approach for characterizing the pathophysiology of WM at various stages, predicting patient risk and monitoring the effectiveness of treatment strategies.