bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis, Structures and Properties of Trioxa[9]circulene and Diepoxycyclononatrinaphthalene
Authors: Yang Daiyue , Cheung Ka Man , Gong Qi , Zhang Li , Qiao Lulin , Chen Xiao , Huang Zhifeng , Miao Qian
Published: April 2024

This article presents trioxa[9]circulene (3) as a novel member of hetero[n]circulenes. Its synthesis began with the synthesis of dimethoxydioxa[8]helicene (5) and used dimethoxydiepoxycyclononatrinaphthalene (4) as a key intermediate, despite the condensation reaction predominantly yielding a 1,4‐addition byproduct. The structures and properties of 3–5 were extensively investigated using experimental and computational methods. Analysis of the crystal structures reveal elongation of the internal C−C bonds in the nine‐membered ring of 3 compared to 4 and 5. Computational studies demonstrate the remarkable flexibility of trioxa[9]circulene's saddle‐shaped polycyclic framework, while the other two compounds are rigid with large racemization barriers. Optically pure forms of 4 and 5 exhibit absorption and luminescence dissymmetry factors on the order of 10−2, with smaller values observed for compound 4. In the crystal structures, molecules of 3 stack to form columns with remarkable π–π overlap, and the π–π interactions of 4 exhibit short intermolecular C‐to‐C contacts. Consequently, the solution‐processed film of 4 functioned as a p‐type organic semiconductor in field effect transistors.
Ionic Covalent Organic Frameworks in Adsorption and Catalysis
Authors: Liu Minghao , Xu Qing , Zeng Gaofeng
Published: April 2024

The ion extraction and electro/photo catalysis are promising methods to address environmental and energy issues. Covalent organic frameworks (COFs) are a class of promising template to construct absorbents and catalysts because of their stable frameworks, high surface areas, controllable pore environments, and well‐defined catalytic sites. Among them, ionic COFs as unique class of crystalline porous materials, with charges in the frameworks or along the pore walls, have shown different properties and resulting performance in these applications with those from charge‐neutral COFs. In this review, current research progress based on the ionic COFs for ion extraction and energy conversion, including cationic/anionic materials and electro/photo catalysis is reviewed in terms of the synthesis strategy, modification methods, mechanisms of adsorption and catalysis, as well as applications. Finally, we demonstrated the current challenges and future development of ionic COFs in design strategies and applications.
Diversified Synthesis of Chiral Fluorinated Cyclobutane Derivatives Enabled by Regio‐ and Enantioselective Hydroboration
Authors: Yuan Fushan , Qi Xingyu , Zhao Yuanyue , Jia Jie , Yan Xufei , Hu Fangdong , Xia Ying
Published: April 2024

The diversified synthesis of chiral fluorinated cyclobutane derivatives has remained a difficult task in synthetic chemistry. Herein, we present an approach for asymmetric hydroboration and formal hydrodefluorination of gem‐difluorinated cyclobutenes through rhodium catalysis, providing chiral gem‐difluorinated α‐boryl cyclobutanes and monofluorinated cyclobutenes with excellent regio‐ and enantioselectivity, respectively. The key to the success of the two transformations relies on an efficient, mild and highly selective rhodium‐catalyzed asymmetric hydroboration with HBPin (pinacolborane), in which the subsequent addition of a base, and a catalytic amount of palladium in some cases, results in the formation of formal hydrodefluorination products with the four‐membered ring retained. The obtained chiral gem‐difluorinated α‐boryl cyclobutanes are versatile building blocks that provide a platform for the synthesis of enantioenriched fluorinated cyclobutane derivatives to a great diversity.
Anion–Cation Competition Chemistry for Comprehensive High‐Performance Prussian Blue Analogs Cathodes
Authors: Cui Mangwei , Zhu Yilong , Lei Hao , Liu Ao , Mo Funian , Ouyang Kefeng , Chen Sheng , Lin Xi , Chen Zuhuang , Li Kaikai , Jiao Yan , Zhi Chunyi , Huang Yan
Published: April 2024

The extensively studied Prussian blue analogs (PBAs) in various batteries are limited by their low discharge capacity, or subpar rate etc., which are solely reliant on the cation (de)intercalation mechanism. In contrast to the currently predominant focus on cations, we report the overlooked anion‐cation competition chemistry (Cl−, K+, Zn2+) stimulated by high‐voltage scanning. With our designed anion‐cation combinations, the KFeMnHCF cathode battery delivers comprehensively superior discharge performance, including voltage plateau >2.0 V (vs. Zn/Zn2+), capacity >150 mAh g−1, rate capability with capacity maintenance above 96 % from 0.6 to 5 A g−1, and cyclic stability exceeding 3000 cycles. We further verify that such comprehensive improvement of electrochemical performance utilizing anion‐cation competition chemistry is universal for different types of PBAs. Our work would pave a new and efficient road towards the next‐generation high‐performance PBAs cathode batteries.
LiDAR Applications in Archaeology: A Systematic Review
Authors: Vinci Giacomo , Vanzani Federica , Fontana Alessandro , Campana Stefano
Published: April 2024

In the last two decades, the analysis of data derived from LiDAR (light detection and ranging) technology has dramatically changed the investigation and documentation of past cultural landscapes, sometimes revealing monumental architectures and settlement systems totally unknown before. Despite the exponential uptick of case studies, an extensive review of LiDAR applications in archaeology is so far missing. Here, we present a systematic survey of works published in international journals in 2001–2022, with the aim of providing an annotated bibliography on the theme and collect quantitative information about each case study. Data collected allowed to analyse the geographic distribution of LiDAR‐based studies, the specifics of acquisitions, the topography and vegetation cover of each study area, the characteristics of the material culture detected, major goals and integrated techniques. The survey considers 291 studies, of which 167 located in Europe, 104 in the Americas and only 20 between Asia, Middle East, Oceania and Africa. Our analysis shows that the impact of LiDAR in archaeological studies was greater in some areas of Europe and North America, where scholars could rely on the availability of open data provided by the institutions. This is testified by the higher number of both case studies and large‐scale projects investigating these regions. It also emerges that LiDAR potential largely depends on the characteristics of the material culture, the vegetation cover and data resolution. These factors underlie the outstanding results achieved through LiDAR in tropical rainforests compared to those obtained in temperate areas, such as the Mediterranean, where the outcropping archaeological evidence, albeit vast and widespread, is generally less preserved and obscured by the dense vegetation of the Mediterranean maquis. We conclude that the increasing availability of LiDAR data over vast areas could lead to enormous advances in the investigation, monitoring and protection of the cultural heritage.
Motivation to learn in university science students studying anatomy: A mixed‐methods analysis of what drives learning
Authors: Willoughby Brooke R. , Flack Natasha A. M. S. , Bird Rebecca J. , Woodley Stephanie J.
Published: April 2024

Exploring student motivation to learn is a research area that has rapidly expanded over the past decade, especially as the COVID‐19 pandemic continues to influence education. In the field of anatomy, most research about motivation to learn targets medical and other health professional students, but little is known about factors that drive students enrolled in science degrees. The aims of this mixed‐methods study were to determine: (1) what motivates undergraduate university science students to learn anatomy, and whether motivation differs between cohorts (second‐ and third‐year) and gender; and (2) the impact of COVID‐19 on motivation to learn. Students (n = 171) completed a survey (the Science Motivation Questionnaire II [SMQII] and questions about learning experiences during the pandemic) and a subset (n = 12) participated in focus groups/interviews. Quantitative data were analyzed using a combination of parametric and non‐parametric statistics, and a general inductive approach was applied to qualitative data. Grade, intrinsic, and career factors were consistently identified as the key components of motivation. No statistically significant differences were found for motivation components between level of study or gender. Students reported that the COVID‐19 pandemic negatively impacted motivational components, but it had also fast‐tracked the development of online learning, with both positive and negative connotations. Students value traditional in‐person lectures but support a blended approach of traditional and online teaching methods for learning anatomy. Educators should utilize these findings when considering how to teach and support science students in ways that embrace motivational components to foster success in those studying anatomy.
A Porphyrin‐Based 3D Metal‐Organic Framework Featuring [Cu8Cl6]10+ Cluster Secondary Building Units: Synthesis, Structure Elucidation, Anion Exchange, and Peroxidase‐Like Activity
Authors: Zeng Chun‐Mei , Luo Song‐Yu , Wang Xiao , Cao Feng‐Lin , Zhang Ze‐Sheng , Zhang Wen‐Hua , Dai Chun‐Lei , Young David J.
Published: April 2024

Herein, we report a rare example of cationic three‐dimensional (3D) metal‐organic framework (MOF) of [Cu5Cl3(TMPP)]Cl5 ⋅ xSol (denoted as Cu−TMPP; H2TMPP=meso‐tetrakis (6‐methylpyridin‐3‐yl) porphyrin; xSol=encapsulated solvates) supported by [Cu8Cl6]10+ cluster secondary building units (SBUs) wherein the eight faces of the Cl−‐based octahedron are capped by eight Cu2+. Surface‐area analysis indicated that Cu−TMPP features a mesoporous structure and its solvate‐like Cl− counterions can be exchanged by BF4−, PF6−, and NO3−. The polyvinylpyrrolidone (PVP) coated Cu−TMPP (denoted as Cu−TMPP−PVP) demonstrated good ROS generating ability, producing ⋅OH in the absence of light (peroxidase‐like activity) and 1O2 on light irradiation (650 nm; 25 mW cm−2). This work highlights the potential of Cu−TMPP as a functional carrier of anionic guests such as drugs, for the combination therapy of cancer and other diseases.
Reliability analysis of δ‐shock models based on the Markovian arrival process
Authors: Goyal Dheeraj , Ali Ramjan , Hazra Nil Kamal
Published: April 2024

The Markovian arrival process (MAP) is a versatile counting process with dependent and non‐identically distributed inter‐arrival times following the phase‐type distribution. In this article, we study the classical ‐shock model and a mixed ‐shock model by assuming the MAP of shocks. We derive explicit expressions for the reliability and the mean lifetime of the system. Further, we study an optimal replacement policy based on the MAP. We illustrate the developed results through several numerical examples.
A study on two‐dimensional warranty with a preventive maintenance policy under burn‐in or run‐in
Authors: Huang Yeu‐Shiang , Fang Chih‐Chiang , Kuo Chia‐Yu
Published: April 2024

Products are often offered with warranties, which have become a common marketing strategy intended to indicate that product quality is guaranteed by the firm. Warranties can attract consumer purchases, but they also incur warranty costs, especially when firms falsely claim that their products are high quality; therefore, the determination of an appropriate warranty policy is of particular importance. This study considers a two‐dimensional warranty for complex repairable products, such as a vehicle, a lathe, or industrial machinery, with consideration of (1) burn‐in (run‐in), which is a supervised accelerating testing process performed before product launch to prevent defective products from being sold on the market, and (2) periodic preventive maintenance, which is performed during the usage period to prevent the occurrence of unexpected failures under normal usage conditions. The optimal burn‐in (run‐in) time and preventive maintenance intervals are determined with the aim of minimizing warranty costs for firms. The results of the study show that given a higher repair cost and a greater infant mortality failure rate, more frequent preventive maintenance is preferable, and the repair cost has the largest effect on the total warranty cost for the firm.
Thermodynamic Understanding of Formation and Evolution of Solid Electrolyte Interface in Li‐Ion Batteries
Authors: He Yitao , Wang Jinkun , Wang Li , He Xiangming
Published: April 2024

Formation is an essential process in the manufacturing of lithium‐ion batteries and determines the performance of batteries, including life time, rate capability and so forth. The core of formation is to form a stable solid electrolyte interphase (SEI), which profoundly influences interfacial reactions and ion transport within Li‐ion batteries, on the surface of electrode. It is crucial to fully and deeply understand the intricate structure and evolution of SEI, which remains largely uncharted. This paper aims to systematically analyze SEI thermodynamics, encompassing energy distribution, entropy dynamics during SEI formation, and enthalpy changes. SEI evolves towards an equilibrium state, maximizing entropy. The intricate relationship between SEI thermodynamics and battery performance is established by dissecting the impacts of temperature and current density on SEI thermodynamic parameters and battery characteristics. Elevated temperatures and higher current densities foster the development of a more porous and high‐entropy outer SEI layer, rendering organic SEI constituents prone to decompose into high‐energy gases and low‐energy inorganic compounds. Notably, a fast formation strategy within a high state‐of‐charge range offers a potential solution to high quality SEI. This review strives to bridge the divide between fundamental thermodynamics and practical battery performance, ultimately contributing to the advancement of battery manufacturing.
Biomolecular phase separation through theoretical and computational microscope
Authors: Kumar Rajeev , Koo Da‐Hyun , Eom Yu‐Gon , Choi Jeong‐Mo
Published: April 2024

Biomolecular phase separation is a vital mechanism for orchestrating biomolecules within living cells. This crucial role has spurred an intense pursuit to comprehend the molecular underpinnings governing and regulating these processes. Computational methodologies offer a unique perspective, augmenting experimental techniques by providing detailed information that cannot be obtained otherwise. In this review, we briefly overview the theoretical and computational approaches to investigate biomolecular phase separation. As a short primer, we explain the factors driving and affecting phase separation of biomolecules, and then we delve into analytical and simulation methods used to study phase separation. We explain how analytical methods like the Flory–Huggins theory, random phase approximation, and graph‐based methods have been used to study phase behaviors of various proteins. We also discuss principles and applications of all‐atom simulations, coarse‐grained simulations, and field‐theoretical approaches. Additionally, we explore the recent advances in machine learning approach to predict phase separation of biomolecules.
Development of a green high‐performance liquid chromatography method for tofacitinib quantification in pharmaceutical formulations and degradation studies
Authors: Tiris Gizem , Genc Asena Ayse , Erk Nevin
Published: April 2024

A new high‐performance liquid chromatography (HPLC) method was applied for the quantification of the active substance of tofacitinib. Analysis was performed on a Chromasil 100 C18 (100.0 × 4.0 mm, 3.5 μm) stationary phase. The mobile phase consisted of acetonitrile:0.2% phosphoric acid in water (12:88, v/v). The prepared sample (20.0 μL) was injected into the system. A detection wavelength of 285.0 nm was chosen for the compound, and the flow rate was 0.8 mL/min. The experiment was completed in 5.0 min. The analysis temperature was set to 40.0°C. The method was evaluated using green chemistry. The method was validated according to the International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use guidelines. For linearity studies calibration curves were constructed in the range of 10.0–200.0 μg/mL. The recovery values were calculated at 97.66% and 105.68%. The method developed for the analysis of the active substance had a short analysis time and was cost‐effective. It is an environmentally friendly method due to the mobile phase content used. The technique can be used in laboratory analysis and bioequivalence experiments.
What are the factors that most influence the formation of workers' labor values in order to achieve sustainable development in Latin America?
Authors: López‐Concepción Arelys , Gil‐Lacruz Ana I. , Saz‐Gil Isabel , Garcia‐Madurga Miguel‐Ángel , Sánchez‐Medalón Ignacio
Published: April 2024

This research delves into the formation of labor values in Latin America, exploring the complex interaction between socio‐demographic characteristics (gender, age, and educational level), well‐being (happiness, health, and life satisfaction), and macroeconomic factors (wealth, equity, and labor market stability). With microdata drawn from the World Values Survey, the study employs Logit and Blinder–Oaxaca decomposition models to analyze data from Brazil, Chile, Colombia, Mexico, and Peru during 2005–2019. It uncovers the significant influence of worker happiness on labor values, especially among self‐employed individuals, and highlights happiness as a critical factor in varying labor values related to different well‐being dimensions. These insights reveal the intricate determinants of work values in the region, providing valuable implications for talent management and policy development aimed at fostering sustainable development through positive labor values.
Stock price reactions to climate science information from the Intergovernmental Panel on Climate Change: A mitigation function of corporate and sector emissions responsibility?
Authors: Teutrine Constanze , Schuster Mario , Bornhöft Sophie Constance , Lueg Rainer , Bouzzine Yassin Denis
Published: April 2024

This research investigates the influence of climate science information released by the Intergovernmental Panel on Climate Change (IPCC) on the European stock market, with a particular emphasis on differentiating the stock price reactions based on sector climate sensitivity and corporate emissions responsibility. Performing an event study on Stoxx Europe 600 constituents, we analyse stock price reactions to the sixth IPCC assessment report published between 2018 and 2023. Results show that climate‐sensitive sectors respond more intensely to climate news. We find greater volatility in stock prices for climate‐sensitive sectors than in corporate emissions‐graded portfolios. Cumulative average abnormal returns range from 26.442% for the alternative energy sector to −6.416% for the construction sector. For the corporate emissions responsibility portfolios, we generally observe negative stock price reactions disregarding firms' level of emissions responsibility. Firms with higher emissions responsibility outperform peers only during the synthesis report release. Our study enriches the literature on stock price reactions to climate science news, which is limited to the analysis of the first five IPCC reports and to sector analyses.
Ultrasound inhibits tumor growth and selectively eliminates malignant brain tumor in vivo
Authors: Buaron Nitsa , Mangraviti Antonella , Wang Yuan , Liu Ann , Pedone Mariangela , Sankey Eric , Adar Itay , Nyska Abraham , Goldbart Riki , Traitel Tamar , Brem Henry , Tyler Betty , Kost Joseph
Published: April 2024

Glioma is one of the most common primary malignant brain tumors. Despite progress in therapeutic approaches, the median survival of patients with glioma remains less than 2 years, generating the need for new therapeutic approaches. Ultrasound (US) is widely used in medical fields and is used as a therapeutic tool mainly for improving the performance of therapeutic entities. In this study, we examined a novel approach using low frequency US (20 kHz) (LFUS) as an independent treatment tool for malignant glioma, since primary studies showed that cancer cells are more susceptible to LFUS than healthy cells. LFUS safety and efficacy were examined in a 9L gliosarcoma‐bearing female Fischer 344 rats. Two LFUS protocols were examined: a one‐time treatment (US1X), and two treatments 24 h apart (US2X). For safety evaluation, rats were monitored for weight change and pain measurements. For efficacy, tumor volume was measured as a function of time and the tumor structural chances were examined histopathologically. LFUS treatment showed rapid inhibition of tumor growth, seen as soon as 12 h after US application. In addition, LFUS was found to affect the tumor structure, which was more extensive (>60% of tumor area) in smaller tumors. In US2X, the tumor tissue was completely destroyed, and an extensive immune response was observed. Importantly, the treatment was highly selective, keeping the healthy tissue surrounding the tumor unharmed. We developed a highly efficient and selective therapeutic protocol for treating malignant glioma with minimal side effects based solely on LFUS.
Association between novel genetic variants of Notch signaling pathway genes and survival of hepatitis B virus‐related hepatocellular carcinoma
Authors: Qin Liming , Qiu Moqin , Lin Qiuling , Jiang Binbin , Zhan Shicheng , Wei Xueyan , Wei Junjie , Liu Yingchun , Wen Qiuping , Chen Peiqin , Jiang Yanji , Zhou Zihan , Liang Xiumei , Cao Ji , Gong Yizhen , Wei Yuying , Wei Xiaoxia , Yu Hongping
Published: April 2024

Background

Although the Notch pathway plays an important role in formation and progression of hepatocellular carcinoma (HCC), few studies have reported the associations between functional genetic variants and the survival of hepatitis B virus (HBV)‐related HCC.

Methods

In the present study, we performed multivariable Cox proportional hazard regression analysis to evaluate associations between 36,101 SNPs in 264 Notch pathway‐related genes and overall survival (OS) of 866 patients with HBV‐related HCC.

Results

It was found that three independent SNPs (NEURL1B rs4868192, CNTN1 rs444927 and FCER2 rs1990975) were significantly associated with the HBV‐related HCC OS. The number of protective genotypes (NPGs) were significantly associated with better survival in a dose‐response manner (ptrend <0.001). Compared with the model with sole clinical factors, the addition of protective genotypes to the predict models significantly increased the AUC, i.e., from 72.72% to 75.13% (p = 0.002) and from 72.04% to 74.76 (p = 0.004) for 3‐year and 5‐year OS, respectively. The expression quantitative trait loci (eQTL) analysis further revealed that the rs4868192 C allele was associated with lower mRNA expression levels of NEURL1B in the whole blood (p = 1.71 × 10‐3), while the rs1990975 T allele was correlated with higher mRNA expression levels of FCER2 in the whole blood and normal liver tissues (p = 3.51 × 10−5 and 0.033, respectively).

Conclusions

Three potentially functional SNPs of NEURL1B, CNTN1 and FCER2 may serve as potential prognostic biomarkers for HBV‐related HCC.
Impact of Fermentation on the Phytochemical Profile and Bioactivity Characteristics of Aqueous Matricaria recutita L. Root Extracts
Authors: Mailänder Lilo K. , Nosrati Gazafroudi Khadijeh , Greiß Marit , Lorenz Peter , Nicolay Sven , Gründemann Carsten , Stintzing Florian C. , Daniels Rolf , Kammerer Dietmar R.
Published: April 2024

While the flowers of Matricaria recutita L., German chamomile, are widely used for medicinal and cosmetic purposes, little is known about its roots, which are used in complementary medicine for the preparation of aqueous fermented extracts for the treatment of cramps and anxiety. To broaden the understanding of the active principles involved, a model fermentation approach was developed and fermentates were compared to commercially manufactured tinctures. Coumarins and hydroxycinnamates were among the major secondary metabolites characterized using HPLC‐MSn. After six months of fermentation and storage, low‐molecular organic acids were detected by GC‐MS. Fermentation contributed to the stabilization of antioxidant and radical scavenging activities, which were in a range of about 8–10 mg gallic acid equivalents/g dry weight and 20–24 mg trolox equivalents/g dry weight, determined by Folin‐Ciocalteu and DPPH assays, respectively. In addition, antibacterial activities of the extracts against Gram‐positive and ‐negative bacteria increased during the first week of fermentation. Fermentates were neither cytotoxic nor pro‐ or anti‐inflammatory. Thus, fermentation of chamomile roots is a suitable method for the safe production of biofunctional aqueous chamomile root extracts that remain stable without the addition of synthetic preservatives.
Bile Salt Hydrolase Activity‐Based Probes for Monitoring Gut Microbial Bile Acid Metabolism
Authors: Han Lin , Xu Raymond , Conwell Amanda N. , Takahashi Sola , Parasar Bibudha , Chang Pamela V.
Published: April 2024

Bile acids are bioactive metabolites that are biotransformed into secondary bile acids by the gut microbiota, a vast consortium of microbes that inhabit the intestines. The first step in intestinal secondary bile acid metabolism is carried out by a critical enzyme, bile salt hydrolase (BSH), that catalyzes the gateway reaction that precedes all subsequent microbial metabolism of these important metabolites. As gut microbial metabolic activity is difficult to probe due to the complex nature of the gut microbiome, approaches are needed to profile gut microbiota‐associated enzymes such as BSH. Here, we develop a panel of BSH activity‐based probes (ABPs) to determine how changes in diurnal rhythmicity of gut microbiota‐associated metabolism affects BSH activity and substrate preference. This panel of covalent probes enables determination of BSH activity and substrate specificity from multiple gut anerobic bacteria derived from the human and mouse gut microbiome. We found that both gut microbiota‐associated BSH activity and substrate preference is rhythmic, likely due to feeding patterns of the mice. These results indicate that this ABP‐based approach can be used to profile changes in BSH activity in physiological and disease states that are regulated by circadian rhythms.
Antimicrobial‐associated encephalopathy due to ampicillin
Authors: Mizutani Naoya , Kenzaka Tsuneaki
Published: April 2024

Key Clinical Message

Because the β‐lactam ring has a molecular structure similar to that of gamma‐aminobutyric acid (GABA) neurotransmitters, it binds to GABA A receptors and inhibits GABAergic transmission, causing AAE. The possibility of antimicrobial‐associated encephalopathy should be considered in cases of neurological or psychiatric symptoms after initiating an antimicrobial regimen.
On the Mechanism of the Lysosomal Enzyme Iduronate‐2‐sulfatase. A Multiscale Approach
Authors: Prejanò Mario , Romeo Isabella , Talerico Cristina , Parise Angela , Russo Nino , Marino Tiziana
Published: April 2024

Iduronate‐2‐sulfatase (IDS) is a Ca2+‐dependent enzyme belonging to the family of sulfatases that catalyzes the hydrolysis of sulphurylated glycosaminoglycans (GAGs), like dermatan and heparan sulphate. Its deficiency or modification leads to the accumulation of GAGs in the human body and to the occurrence of severe conditions, such as Hunter disease, or Mucopolysaccharidosis type II. Due to its involvement in this syndrome, it is of interest to understand the action mechanism of the enzyme to design new drugs for more efficient medical strategies. In the present work, we carried out a detailed multiscale modelling‐based investigation, adopting molecular dynamics simulation (MDs) and QM/MM calculations to study the enzyme‐dermatan sulfate interactions and to investigate the reaction mechanism of IDS. The analysis of molecular dynamics trajectories helped to shed light on the contribution of the individual residues of the active site in the recognition of dermatan sulfate. The role of FGly84 and His229, investigated in both neutral and protonated states in the case of the latter, is highlighted for the binding of the substrate. QM/MM calculations demonstrated that the reaction mechanism is a two‐steps process occurring via a sulphurylation‐desulphurylation mechanism where the FGly84 first attacks the sulphate group of the dermatan sulphate (DS), and later is desulphurylated.
Selective Transition Enhancement in a g‐Engineered Diradical
Authors: Komeda Joe , Boudalis Athanassios K. , Montenegro‐Pohlhammer Nicolas , Antheaume Cyril , Mizuno Asato , Turek Philippe , Ruben Mario
Published: April 2024

A diradical with engineered g‐asymmetry was synthesized by grafting a nitroxide radical onto the [Y(Pc)2]⋅ radical platform. Various spectroscopic techniques and computational studies revealed that the electronic structures of the two spin systems remained minimally affected within the diradical system. Fluid‐solution Electron Paramagnetic Resonance (EPR) experiments revealed a weak exchange coupling with |J| ~ 0.014 cm−1, subsequently rationalized by CAS‐SCF calculations. Frozen solution continuous‐wave (CW) EPR experiments showed a complicated and power‐dependent spectrum that eluded analysis using the point‐dipole model. Pulse EPR manipulations with varying microwave powers, or under varying magnetic fields, demonstrated that different resonances could be selectively enhanced or suppressed, based on their different tipping angles. In particular, Field‐Swept Echo‐Detected (FSED) spectra revealed absorptions of MW power‐dependent intensities, while Field‐Swept Spin Nutation (FSSN) experiments revealed two distinct Rabi frequencies. This study introduces a methodology to synthesize and characterize g‐asymmetric two‐spin systems, of interest in the implementation of spin‐based CNOT gates.
Indenoannulated Tridecacyclene: An All‐Carbon Seven‐Stage Redox‐Amphoter
Authors: Misselwitz Erik , Spengler Jonas , Rominger Frank , Kivala Milan
Published: April 2024

We disclose an indenoannulated tridecacyclene comprising a central cyclooctatetraene moiety with multiple adjacent pentagonal rings which is accessible in a concise synthetic sequence. The saddle‐shaped geometry of the non‐benzenoid polycyclic scaffold and its unique packing behavior in the solid state were characterized by X‐ray crystallography. In electrochemical studies, the compound undergoes seven reversible redox events comprising five reductions and two oxidations. The dicationic and dianionic species obtained by chemical oxidation and reduction, respectively, were characterized spectroscopically in solution. Density functional theory calculations were applied to provide insights into aromaticity evolution in the respective charged species, highlighting the beneficial effect of the non‐benzenoid moieties on charge stabilization
Advances in the Continuous Flow Synthesis of 3‐ and 4‐Membered Ring Systems
Authors: Donnelly Kian , Baumann Marcus
Published: April 2024

Small carbo‐ and heterocyclic ring systems have experienced a significant increase in importance in recent years due to their relevance in modern pharmaceuticals, as building blocks for designer materials or as synthetic intermediates. This necessitated the development of new synthetic methods for the preparation of these strained ring systems focusing on effectiveness and scalability. The high ring strain of these entities as well as the use of high‐energy reagents and intermediates has often challenged their synthesis. Continuous flow approaches have thus emerged as highly effective means to safely and reliably access these strained scaffolds. In this short review, key developments in this field are summarised showcasing the power of continuous flow approaches for accessing 3‐ and 4‐membered ring systems via thermal, photo‐ and electrochemical processes.
PROTOCOL: Key characteristics of effective preschool‐based interventions to promote self‐regulation: A systematic review and meta‐analysis
Authors: Kanayama Atsushi , Siraj Iram , Moeyaert Mariola , Steiner Kat , Yu Elie ChingYen , Ereky‐Stevens Katharina , Iwasa Kaoru , Ishikawa Moeko , Kahlon Mehar , Warnatsch Rahel , Dascalu Andreea , He Ruoying , Mehta Pinal P. , Robinson Natasha , Shi Yining
Published: April 2024

This is the protocol for a Campbell Systematic Review. The objectives are as follows: The aim of this systematic review is to advance our understanding of the key characteristics of effective preschool‐based interventions designed to foster self‐regulation. To accomplish this, the review addresses the following questions: 1. What types of preschool‐based interventions have been developed to promote self‐regulation? 2. What is the average effect of these preschool‐based interventions on self‐regulation, focusing on four key constructs: integrative effortful control, integrative executive function, self‐regulation, and self‐regulated learning? 3. What characteristics—such as Resource Allocation, Activity Type, and Instruction Method—could potentially contribute to the effects of preschool‐based interventions in promoting self‐regulation?
Cabozantinib with immune checkpoint inhibitor versus cabozantinib monotherapy in patients with metastatic clear cell renal cell carcinoma progressing after prior immune checkpoint inhibitor
Authors: Gebrael Georges , Jo Yeonjung , Mathew Thomas Vinay , Li Haoran , Sayegh Nicolas , Tripathi Nishita , Srivastava Ayana , Nordblad Blake , Dal Emre , Narang Arshit , Brundage James , Campbell Patrick , Galarza Fortuna Gliceida , Hage Chehade Chadi , Maughan Benjamin L. , Agarwal Neeraj , Swami Umang
Published: April 2024

Introduction

Rechallenge with antibodies targeting programmed cell death protein‐1 or its ligand (PD‐1/L1) after discontinuation or disease progression in solid tumors following a prior PD‐1/L1 treatment is often practiced in clinic. This study aimed to investigate if adding PD‐1/L1 inhibitors to cabozantinib, the most used second‐line treatment in real‐world patients with metastatic clear cell renal cell carcinoma (mccRCC), offers additional benefits.

Methods

Using de‐identified patient‐level data from a large real‐world US‐based database, patients diagnosed with mccRCC, who received any PD‐1/L1‐based combination in first‐line (1L) setting, followed by second‐line (2L) therapy with either cabozantinib alone or in combination with PD‐1/L1 inhibitors were included. Patients given a cabozantinib‐containing regimen in 1L were excluded. The study end points were real‐world time to next therapy (rwTTNT) and real‐world overall survival (rwOS) by 2L.

Results

Of 12,285 patients with metastatic renal cell carcinoma in the data set, 348 patients met eligibility and were included in the analysis. After propensity score matching weighting, cabozantinib with PD‐1/L1 inhibitors versus cabozantinib (ref.) had similar rwTTNT and rwOS in the 2L setting. Hazard ratios and 95% confidence interval (CI) for rwTTNT and rwOS are 0.74 (95% CI, 0.49–1.12) and 1.15 (95% CI, 0.73–1.79), respectively.

Conclusion

In this study, the results align with the phase 3 CONTACT‐03 trial results, which showed no additional benefit of adding PD‐L1 inhibitor to cabozantinib compared to cabozantinib alone in 2L following PD‐1/L1–based therapies in 1L. These results from real‐world patients strengthen the evidence regarding the futility of rechallenge with PD‐1/L1 inhibitors.
Molecular analysis using SalvGlandDx improves risk of malignancy estimation and diagnosis of salivary gland cytopathology: An exploratory multicenter study
Authors: Freiberger Sandra N. , Ikenberg Kristian , van Egmond Demi , Claerhout Sofie , van Wezel Tom , Bempt Isabelle Vanden , van Rossem Jeroen N. , Mueller Simon A. , Clement Paul M , Poorten Vincent Vander , Cohen Danielle , Hauben Esther , Rupp Niels J.
Published: April 2024

Background

Diagnosis of salivary gland neoplasms is challenging, especially on cytological specimens acquired by fine‐needle aspiration. The recently implemented standardized Milan system for reporting salivary gland cytopathology provides an estimated risk of malignancy (ROM); yet, for two of the categories, the diagnosis of the lesion remains unclear. However, a precise diagnosis is desirable for optimal patient management, including planning of surgery and imaging procedures.

Methods

Cytological specimens (n = 106) were subjected to molecular analysis using the SalvGlandDx panel. The risk of malignancy was calculated for each detected alteration based on the diagnosis of the resection specimen. By taking into account the molecular alterations, their associated ROM, the clinical and cytological features, and the current literature, the Milan category was evaluated.

Results

Of n = 63 technically valid cases, 76% revealed a molecular alteration. A total of 94% of these molecularly altered cases could be assigned to a different Milan category when additionally taking molecular results into account. In only 2% of the salivary gland neoplasms of uncertain malignant potential, in which a molecular alteration was detected, the classification remained salivary gland neoplasms of uncertain malignant potential.

Conclusion

Molecular analysis of cytological specimens provides a benefit in classifying salivary gland neoplasms on fine‐needle aspiration. It can improve the ROM estimation and thus help to assign cases of formerly unknown malignant potential to clearly benign or malignant categories.
Sustainability reporting quality in Malaysia: The intricacy of family controlled and politically connected firms
Authors: Elaigwu Moses , Abdulmalik Salau Olarinoye , Alghorbany Abdelkader , Che‐Ahmad Ayoib
Published: April 2024

The study contributes to the existing literature by examining the relationship between family‐controlled firms (FCFs), politically connected firms (PCFs), and sustainability reporting quality (SRQ) in Malaysia. The study utilizes panel regression techniques to test the hypotheses. The study's findings revealed that FCFs have a significant negative effect on SRQ. On the other hand, PCFs show a positive significant effect on SRQ. Moreover, the study uncovers a significant and positive interacting effect of PCFs in the relationship between FCFs and SRQ. The implication of this is that politically connected family‐controlled firms (PCFCFs) exhibit higher levels of sustainability performance and disclosure quality. The study offers valuable implications for regulators, scholars, and practitioners. Policymakers can use the insights from this paper to develop regulations and guidelines that encourage family‐controlled firms to improve the quality of their sustainability disclosures. Furthermore, the study provides a foundation for further research in this domain to confirm the result of the present investigation.
Unlocking sustainability potential: The impact of green finance reform on corporate ESG performance
Authors: Gao Da , Zhou Xiaotian , Wan Jing
Published: April 2024

Improving the incentive mechanism and institutional framework of green finance policy is important to promote the synchronization of environmental management and enterprise development. Based on China's green finance reform and innovation pilot (GFRIP) policy in 2017, this study constructs a quasi‐natural experiment with a sample of A‐share listed companies and draws the following conclusions. (1) The effectiveness of GFRIP policy in significantly promoting enterprises' ESG performance in pilot areas, robustness tests such as propensity score matching and placebo tests reconfirm conclusions. (2) The GFRIP policy can effectively improve enterprise ESG performance by easing financing constraints, promoting green investment, and improving managers' green cognition. (3) Both external environmental law enforcement and internal manager environmental awareness can enhance the promotion effect of the GFRIP policy on ESG performance. (4) Heterogeneity analysis shows that the ESG performance of state‐owned enterprises, large enterprises, and high‐polluting enterprises is more affected by pilot policy. The results of the study provide a valuable perspective on how the government can promote green finance policies and implications for enterprises' sustainable development.
Circularly polarized implantable MIMO antenna for skin, brain and heart implantation with wide axial ratio bandwidth
Authors: Kangeyan Rajagopal , Karthikeyan Madurakavi
Published: April 2024

A unique MIMO antenna with circular polarization characteristics that works similarly for skin, brain and heart phantoms has been proposed in this paper. The twin rectangular X‐shaped slot that serves as the basic structure of the proposed antenna is entirely planar and low‐profile but has a defective ground plane. For three different phantoms, the proposed antenna resonates at 2.4–2.45 GHz ISM band. With a dimension of
, the antenna exhibits compactness. Rogers RT/duroid 6010 substrate material has been used to fabricate the antenna in order to validate the designed antenna structure. Utilizing the high dielectric material for both substrate and superstrate, both skin‐mimicking gel and minced hog meat were employed in the experiment setup at 2.45 GHz ISM band. At ISM band, −28.3 dBi has been observed has realized peak gain. The obtained fractional bandwidth (FBW) and Axial Ratio Bandwidth (ARBW) values are 30.67% and 45%, respectively. Also, the maximum specific absorption rate (SAR) values are found to be in the acceptable limit regulated by IEEE.
Bedrock morphology influences rock barrens turtle nesting habitat energy dynamics
Authors: Van Huizen Brandon , Markle Chantel E. , Moore Paul A. , Waddington James M.
Published: April 2024

Energy absorption and flow through a nest is an important aspect of embryonic development in many reptile species including turtles. To date, few studies have explicitly attempted to quantify the energy flow through turtle nests, opting instead for the simplified approach offered by temperature index models. However, the quantification of the energy can provide an explicit abiotic link that can link biological models to biometeorological and ecohydrological processes and models. We investigated the energy flow through turtle nests occupying different bedrock morphologies within a Canadian Shield Rock Barren landscape, in Ontario, Canada. The taxons studied were Spotted Turtle (Clemmys guttata), Midland Painted Turtle (Chrysemys picta marginata), and Blanding's Turtle (Emydoidea blandingii). Nest temperature and soil moisture were measured in 2018 and 2019 using sensors placed in the soil adjacent to 12 turtle nest cavities. Three main rock morphologies were identified for each nest location, Crevice, Ledge, and Flat types, that are in order of decreasing bedrock percentage contact with the nest site. Ground heat flux and change in heat storage were determined using the calorimetric method for each nest, while the direction of energy flux between the atmosphere and the underlying rock was also determined. The Crevice nest morphology experienced the lowest ground heat flux on average (1.56 × 10−1 W m−2) and lowest cumulative heat storage (230 MJ) compared to the Flat (440 MJ) and Ledge (331 MJ) nests. However, over the diurnal cycle, large heat gains by Flat nests were mostly balanced out by nighttime heat losses. While Crevice nests saw the lowest daily heat storage gains, they experienced much lower heat losses over the evening period compared to the other nest types. Furthermore, we found that 59% of the energy is directed from the underlying bedrock into the Crevice nest, highlighting the importance of the bedrock in controlling thermal dynamics in the turtle nesting habitat. The lower variability in energy parameters for Crevice nest types can be attributed to higher amounts of nest‐to‐bedrock contact, compared to the flat nest types. Our results indicate that Crevice morphology may be ideal for turtles nesting at their northern limits because minimal heat loss during the evening can result in a more stable thermal incubation environment. Future conservation and habitat restoration efforts should consider the importance of bedrock morphology and prioritize the protection of Crevice nest sites. Furthermore, this work highlights important opportunities for potential interdisciplinary work between ecologists, climatologists, biologists, and hydrologists, specifically the integration of ecohydrological and biological models. This work also underscores the potential uncertainty of climate change impacts on turtle egg hatching success and nest sex ratios.
Natural mating ability is associated with gut microbiota composition and function in captive male giant pandas
Authors: Yan Zheng , Lei Yinghu , Zhao Pengpeng , Zhang Danhui , Shen Jiena , Zhang Guiquan , Wei Rongping , Liu Haoqiu , Liu Xiaoyan , He Yan , Shen Sijia , Liu Dingzhen
Published: April 2024

The issue of poor sexual performance of some male giant pandas seriously impairs the growth and the genetic diversity of the captive population, yet there is still no clear understanding of the cause of the loss of this ability and its underlying mechanism. In this study, we analyzed the gut microbiota and its function in 72 fecal samples obtained from 20 captive male giant pandas, with an equal allocation between individuals capable and incapable of natural mating. Additionally, we investigated fecal hormone levels and behavioral differences between the two groups. A correlation analysis was then conducted among these factors to explore the influencing factors of their natural mating ability. The results showed significant differences in the composition of gut microbiota between the two groups of male pandas. The capable group had significantly higher abundance of Clostridium sensu stricto 1 (padjusted = .0021, GLMM), which was positively correlated with fatty acid degradation and two‐component system functions (Spearman, padjusted < .05). Additionally, the capable group showed higher gene abundance in gut microbiota function including purine and pyrimidine metabolism and galactose metabolism, as well as pathways related to biological processes such as ribosome and homologous recombination (DEseq2, padjusted < .05). We found no significant differences in fecal cortisol and testosterone levels between the two groups, and no difference was found in their behavior either. Our study provides a theoretical and practical basis for further studying the behavioral degradation mechanisms of giant pandas and other endangered mammal species.
Tonic immobility behaviour does not differ between fire salamander larvae from ponds and streams
Authors: Schulte Laura , Caspers Barbara A.
Published: April 2024

Tonic immobility is an antipredator defence in which the prey animal remains motionless after physical contact with the predator, pretending to be dead. This behaviour has been observed among a variety of taxa but has received only little attention in amphibian larvae. During our field studies with fire salamander larvae, we observed that larvae from different habitats display tonic immobility after handling. In our study site, we find larvae in pond and stream habitats, that differ in several aspects such as their stress response and their risk‐taking behaviour, likely caused by the very different habitat conditions. We measured the time that the tonic immobility behaviour was displayed but found no difference between larvae from the two habitat types. Likewise, we also found no correlation between the size of the larvae and the duration of displaying the behaviour. In conclusion, we found that fire salamander larvae show tonic immobility, but found no evidence that the different habitat conditions influence the tonic immobility behaviour.