bluuebunny/crossref_metadata_2025 huggingface dataset:
Sustainable Hierarchically Porous Reusable Metal–Organic Framework Sponge as a Heterogeneous Catalyst and Catalytic Filter for Degradation of Organic Dyes
Authors: Du Yingying , Ding Chenhui , Agarwal Seema
Published: December 2023

Advanced oxidation processes based on sulfate radical are considered one of the most promising wastewater treatment technologies currently. Among heterogeneous catalysts, cobalt metal–organic framework (MOF) has been widely reported. However, the inherent powder form of MOF hinders its practical application and reusability. Therefore, innovative methods to increase the loading capacity and the accessibility of MOF active sites in monolithic materials are required. Therefore, a simple and scalable method of fabricating a stable, hierarchical porous zeolitic imidazolate framework (ZIF‐67) 3D sponge by growing MOF on a short electrospun fiber network is shown. The sponge can efficiently activate peroxymonosulfate and rapidly degrade an exemplary organic dye (Rhodamine B) with a degradation efficiency of 100%. The resulting multilevel, hierarchical porous structure is beneficial to the mass transfer of reagents making the catalytic process efficient. This also enables the use of the ZIF‐67 as an efficient catalytic filter for continuous removal of dye. The sponge can be recycled and reused for several cycles due to its robustness without loss in efficiency. The proposed research strategy provides a new way to design MOF 3D monolithic materials.
Response of yellow perch to water level fluctuations in oligotrophic, north‐temperate inland lakes
Authors: Shay Gabrielle P. , Sass Greg G. , Mrnak Joseph T.
Published: December 2023

Information on yellow perch Perca flavescens population dynamics and responses to various abiotic and biotic factors in oligotrophic, north‐temperate inland lakes is limited. Water level fluctuations are known to influence available habitat and biological communities within the littoral zones of lakes, yet research is lacking for yellow perch in Wisconsin. The goal of our study was to characterize yellow perch population‐level responses to natural water level fluctuations in four northern Wisconsin lakes using a 39‐year time series. On average, increasing water level periods correlated with lower mean fyke net and gill net relative abundances (catch‐per‐unit‐effort), though generally not statistically significant. Yellow perch mean relative weight varied among lakes and was significantly greater during increasing water level periods for all lakes except one. The lack of statistically significant findings potentially suggests a buffering mechanism of north‐temperate oligotrophic lakes due to their small surface area to volume ratios, relative lack of nutrients, and(or) littoral structural habitat compared to other systems (e.g., shallow eutrophic lakes). Our results suggest that natural water level fluctuations may not be an environmental concern for yellow perch populations in some north‐temperate oligotrophic inland lakes.
Harmonization of four biomarkers across nine nationally representative studies of older persons
Authors: Hu Peifeng , Crimmins Eileen M. , Kim Jung Ki , Potter Alan , Cofferen Jake , Merkin Sharon , McCreath Heather , Seeman Teresa
Published: December 2023

Introduction

A growing number of international population surveys have included measurement of biomarkers, but differ in the type of specimens collected, sample processing procedures, shipment protocols, and laboratory assay platforms. The purpose of this study is to harmonize biomarker data from nine nationally representative studies of people 50 years of age and over by adjusting for assay platforms and type of specimens for total cholesterol (total‐C), high‐density lipoprotein cholesterol (HDL‐C), glycosylated hemoglobin (HbA1c), and C‐reactive protein (CRP).

Methods

Sets of 24 identical serum, plasma, whole blood, and dried blood spot harmonization samples with known analyte levels were generated at a reference laboratory, shipped at −80°C to the respective study laboratories, and subsequently assayed following the study laboratory's protocol. Both original and harmonized study data were used to calculate mean values and at‐risk prevalence.

Results

The correlation coefficients between the biomarker values of the harmonization samples obtained by the study laboratories and the reference laboratory were 0.99 or above for all analytes and laboratories, indicating the high quality of assays at all laboratories. However, using the harmonized data from each study, there were significant differences in the mean values and country ranking of the prevalence of at‐risk levels of these four biomarkers.

Conclusions

While the biomarker data from the different study laboratories were highly correlated, indicating very high correlation of rank order of specimens, absolute values did vary significantly. This can have a major impact on assessment of international differences in estimates of risks for chronic morbidity and mortality.
A patient with Pitt–Hopkins syndrome with concomitant common variable immunodeficiency
Authors: Malik Shahzara , Jeanpierre Latoya , Cianferoni Antonella , Ruffner Melanie , Sullivan Kathleen E.
Published: December 2023

In patients with 18q deletion syndrome (18q‐), immunodeficiency, autoimmunity, and allergies have been described in a subset. Pitt–Hopkins syndrome represents a specific subset of patients with 18q‐ who have a proximal deletion involving the TCF4 gene or a TCF4 variant. Immunodeficiency has been reported in the overall 18q‐ population; however, immunodeficiency with Pitt‐Hopkins syndrome has not been highlighted. This case report details the immunologic evaluations and the associated infections seen in a young adult with Pitt–Hopkins syndrome to underscore the challenges of managing adults with a complex phenotype who develop frequent infections. This patient with Pitt–Hopkins syndrome ultimately fulfilled the diagnostic criteria for common variable immunodeficiency. Immunoglobulin replacement has led to a somewhat improved infection pattern, although she continues to have aspiration events leading to pneumonia. This case highlights the clinical evolution of Pitt–Hopkins syndrome and serves as a reminder that immunodeficiency can occur in this syndrome.
Genetic counselors' utilization of ChatGPT in professional practice: A cross‐sectional study
Authors: Ahimaz Priyanka , Bergner Amanda L. , Florido Michelle E. , Harkavy Nina , Bhattacharyya Sriya
Published: December 2023

Purpose

The precision medicine era has seen increased utilization of artificial intelligence (AI) in the field of genetics. We sought to explore the ways that genetic counselors (GCs) currently use the publicly accessible AI tool Chat Generative Pre‐trained Transformer (ChatGPT) in their work.

Methods

GCs in North America were surveyed about how ChatGPT is used in different aspects of their work. Descriptive statistics were reported through frequencies and means.

Results

Of 118 GCs who completed the survey, 33.8% (40) reported using ChatGPT in their work; 47.5% (19) use it in clinical practice, 35% (14) use it in education, and 32.5% (13) use it in research. Most GCs (62.7%; 74) felt that it saves time on administrative tasks but the majority (82.2%; 97) felt that a paramount challenge was the risk of obtaining incorrect information. The majority of GCs not using ChatGPT (58.9%; 46) felt it was not necessary for their work.

Conclusion

A considerable number of GCs in the field are using ChatGPT in different ways, but it is primarily helpful with tasks that involve writing. It has potential to streamline workflow issues encountered in clinical genetics, but practitioners need to be informed and uniformly trained about its limitations.
Development and validation of a computable phenotype for Turner syndrome utilizing electronic health records from a national pediatric network
Authors: Huang Sarah D. , Bamba Vaneeta , Bothwell Samantha , Fechner Patricia Y. , Furniss Anna , Ikomi Chijioke , Nahata Leena , Nokoff Natalie J. , Pyle Laura , Seyoum Helina , Davis Shanlee M.
Published: December 2023

Turner syndrome (TS) is a genetic condition occurring in ~1 in 2000 females characterized by the complete or partial absence of the second sex chromosome. TS research faces similar challenges to many other pediatric rare disease conditions, with homogenous, single‐center, underpowered studies. Secondary data analyses utilizing electronic health record (EHR) have the potential to address these limitations; however, an algorithm to accurately identify TS cases in EHR data is needed. We developed a computable phenotype to identify patients with TS using PEDSnet, a pediatric research network. This computable phenotype was validated through chart review; true positives and negatives and false positives and negatives were used to assess accuracy at both primary and external validation sites. The optimal algorithm consisted of the following criteria: female sex, ≥1 outpatient encounter, and ≥3 encounters with a diagnosis code that maps to TS, yielding an average sensitivity of 0.97, specificity of 0.88, and C‐statistic of 0.93 across all sites. The accuracy of any estradiol prescriptions yielded an average C‐statistic of 0.91 across sites and 0.80 for transdermal and oral formulations separately. PEDSnet and computable phenotyping are powerful tools in providing large, diverse samples to pragmatically study rare pediatric conditions like TS.
Organocatalyzed Synthesis of Bicyclic γ‐Lactam Derivatives via Asymmetric Conjugate Addition of Cyclic β‐Keto Esters to Benzoyl Acrylonitriles
Authors: Matsushima Yasuyuki , Kubokawa Satsuki , Watanabe Mia , Nakashima Kosuke , Hirashima Shin‐ichi , Miura Tsuyoshi
Published: December 2023

A diaminomethylenemalononitrile organocatalyst efficiently promoted the asymmetric conjugate addition of cyclic β‐keto esters to benzoyl acrylonitriles to afford the corresponding adducts. This was followed by the transformation of the nitrile group into an amide group, resulting in bicyclic γ‐lactam derivatives in good yields with excellent enantioselectivities (up to 99 % ee). As far as we know, this is the first study to synthesize chiral bicyclic γ‐lactam derivatives from cyclic β‐keto esters and benzoyl acrylonitriles.
One Collision—Two Substituents: Gas‐Phase Preparation of Xylenes under Single‐Collision Conditions
Authors: Medvedkov Iakov A. , Nikolayev Anatoliy A. , He Chao , Yang Zhenghai , Mebel Alexander M. , Kaiser Ralf I.
Published: December 2023

The fundamental reaction pathways to the simplest dialkylsubstituted aromatics—xylenes (C6H4(CH3)2)—in high‐temperature combustion flames and in low‐temperature extraterrestrial environments are still unknown, but critical to understand the chemistry and molecular mass growth processes in these extreme environments. Exploiting crossed molecular beam experiments augmented by state‐of‐the‐art electronic structure and statistical calculations, this study uncovers a previously elusive, facile gas‐phase synthesis of xylenes through an isomer‐selective reaction of 1‐propynyl (methylethynyl, CH3CC) with 2‐methyl‐1,3‐butadiene (isoprene, C5H8). The reaction dynamics are driven by a barrierless addition of the radical to the diene moiety of 2‐methyl‐1,3‐butadiene followed by extensive isomerization (hydrogen shifts, cyclization) prior to unimolecular decomposition accompanied by aromatization via atomic hydrogen loss. This overall exoergic reaction affords a preparation of xylenes not only in high‐temperature environments such as in combustion flames and around circumstellar envelopes of carbon‐rich Asymptotic Giant Branch (AGB) stars, but also in low‐temperature cold molecular clouds (10 K) and in hydrocarbon‐rich atmospheres of planets and their moons such as Triton and Titan. Our study established a hitherto unknown gas‐phase route to xylenes and potentially more complex, disubstituted benzenes via a single collision event highlighting the significance of an alkyl‐substituted ethynyl‐mediated preparation of aromatic molecules in our Universe.
Rational Design and Reticulation of Infinite qbe Rod Secondary Building Units into Metal–Organic Frameworks through a Global Desymmetrization Approach for Inverse C3H8/C3H6 Separation
Authors: Gong Wei , Xie Yi , Yamano Akihito , Ito Sho , Reinheimer Eric W. , Dong Jinqiao , Malliakas Christos D. , Proserpio Davide M. , Cui Yong , Farha Omar K.
Published: December 2023

The development of reticular chemistry has enabled the construction of a large array of metal–organic frameworks (MOFs) with diverse net topologies and functions. However, dominating this class of materials are those built from discrete/finite secondary building units (SBUs), yet the designed synthesis of frameworks involving infinite rod‐shaped SBUs remain underdeveloped. Here, by virtue of a global linker desymmetrization approach, we successfully targeted a novel Cu‐MOF (Cu‐ASY) incorporating infinite Cu‐carboxylate rod SBUs with its structure determined by micro electron diffraction (MicroED) crystallography. Interestingly, the rod SBU can be simplified as a unique cylindric sphere packing qbe tubule made of [43.62] tiles, which further connect the tritopic linkers to give a newly discovered 3,5‐connected gfc net. Cu‐ASY is a permanent ultramicroporous material featuring 1D channels with highly inert surfaces and shows a preferential adsorption of propane (C3H8) over propene (C3H6). The efficiency of C3H8 selective Cu‐ASY is validated by multicycle breakthrough experiments, giving C3H6 productivity of 2.2 L/kg. Density functional theory (DFT) calculations reveal that C3H8 molecules form multiple C−H⋅⋅⋅π and atypical C−H⋅⋅⋅ H−C van der Waals interactions with the inner nonpolar surfaces. This work therefore highlights the linker desymmetrization as an encouraging and intriguing strategy for achieving unique MOF structures and properties.
Evaluation of the influence of adding clay in polymeric hydrogels based on partially hydrolyzed polyacrylamide and aluminum citrate
Authors: Neto Venâncio J. S. , Dores Felipe G. L. , Oliveira Priscila F. , Mansur Claudia R. E.
Published: December 2023

Polymeric hydrogels have been evaluated for their ability to block high‐permeability regions of heterogeneous reservoirs, distributing the injected fluids to low‐permeability regions, aiming to improve oil recovery. However, the stability of these hydrogels can be reduced under conditions of high temperature and salinity typical of reservoirs. Thus, the objective of this study was to assess the properties of hydrogels based on partially hydrolyzed polyacrylamide, with different molar masses, crosslinked with aluminum citrate, in the presence or absence of bentonite clay. We call these systems composite hydrogels or conventional hydrogels, respectively, and prepared them in synthetic brine containing 29,940 mg/L of total dissolved solids. The selected hydrogels were submitted to rheology tests and scanning electron microscopy for assignment of gel strength codes. The results showed it was possible to obtain composite hydrogels with enhanced thermal properties in comparison with conventional hydrogels, mainly at a temperature of 85°C. The rheological tests, by determining the viscous modulus (G"), elastic modulus (G'), and the ratio between the two (G"/G'), along with the tan δ factor, indicated competition in the interaction between the clay and crosslinker, due to the latter's positive charges in relation to the negative charges present in the polymer chains. The scanning electron microscopy micrographs showed the presence of clay particles adhered in the polymer chain, improving the thermal resistance of the system.
Reconfigurable and Phase‐Engineered Acoustic Metasurfaces for Broadband Wavefront Manipulation
Authors: Zeng Kexin , Li Zhendong , Guo Zichao , Wang Zhonggang
Published: December 2023

A novel type of phase‐engineered acoustic metasurfaces with reconfigurable properties is reported, enabling the flexible broadband manipulation of reflected wavefronts. The participants of the metasurface are elements conceived to possess even‐distributed reflected phases covering 2π span with linearity and small acoustic energy loss. The reconfigurable property of the metasurface is implemented by rearranging the fixed meta‐elements based on the phase profile, which is related to the characteristic of a specific wavefront shape. The metasurface's capability is successfully demonstrated to achieve acoustic focusing and bending within the frequency range of 2300–2800 Hz, showcasing its feasibility and adaptability. To enhance its practical applications, porous materials are incorporated, leveraging the robustness of phase differences among the meta‐elements to achieve high acoustic energy cancellation. Effective sound attenuation occurs within the frequency range of 1300–3100 Hz, even under wide‐angle incidences ranging from −80° to 80°. The work paves the way for further research on reconfigurable acoustic metasurfaces in broad frequency regions and exerts favorable implications for generally applicable structures applied in multi‐fields including biomedical acoustics, noise control, and so on.
Boosting Peroxymonosulfate Activation via CoS/MXene Nanocomposite for Rhodamine B Degradation under Simulated Sunlight Irradiation
Authors: Wu Yizhou , Zhao Qingzi , Wang Jia , Lu Sitong , Zhou Liang , Lei Juying , Zhang Jinlong , Liu Yongdi
Published: December 2023

Cobalt‐based heterogeneous catalysts have been demonstrated as an effective PMS activator for pollutant degradation. However, the limited active sites on their surface lead to an unsatisfactory catalytic efficiency. Immobilizing the catalysts on the support material can be a promising modification strategy to solve this problem. MXene has been considered as an ideal support material due to its unique morphology and physicochemical properties. Therefore, in this work, the CoS‐loaded Ti3C2 MXene (CoS/Ti3C2 MXene) catalyst for peroxymonosulfate (PMS) activation was successfully synthesized through a solvothermal method. Under the simulated sunlight irradiation, the CoS/Ti3C2 MXene+PMS system achieved an impressive efficiency in removing the organic pollutant rhodamine B (97.2 % in 10 min). Among the tested catalysts, 30 %‐CoS‐TC stood out, exhibited a broad pH tolerance from 5 to 9 and maintained robust degradation performance over cycles. Upon detailed analysis, the degradation mechanism revealed the collaborative action dominated by singlet oxygen, and supplemented by photogenerated holes and superoxide radicals in the process. Notably, the sandwich‐like structure of MXene played a pivotal role, not only dispersing the CoS particles evenly on the surface of catalysts, but also providing ample space for the active sites, thus accelerating the PMS activation for the degradation of rhodamine B. Overall, this study developed an innovative MXene‐based catalyst for the application of environmental remediation.
A geometric key for enhancing the radiative efficiency of ortho‐carboranyl luminophores: Indolocarbazole‐ and m‐terphenyl‐ortho‐carboranes
Authors: Kim Mingi , Cho Kanghee , Seo Yung Ju , Choi Junhyeok , Kim Namkyun , Shin Ilsup , Lee Kang Mun
Published: December 2023

In this study, we introduce two ortho‐carboranyl compounds, namely ICzCB and mTPCB, which exhibit different planarity in their appended π‐conjugated aromatic groups, to investigate the influence of geometric effects on the regulation of the radiative efficiency. Both the compounds are fully characterized, revealing distinct geometric differences (planarity) in their single‐crystal structures. While ICzCB presents strong ICT‐based emission in the solid (film) state, mTPCB displays dual emission in the high‐ and low‐energy regions that originates from locally excited (LE)‐ and ICT‐based processes, respectively. Quantitative analysis of the photophysical characteristics of the compounds shows that the ICT‐based radiative efficiency in ICzCB is higher than that in mTPCB. Consequently, these findings demonstrate that the planarity of the π‐conjugated aryl group appended on o‐carborane, which is represented by planar ICzCB and distorted mTPCB, is an important key to control the ICT‐based radiative decay efficiency.
Immune checkpoint status and exhaustion‐related phenotypes of CD8+ T cells from the tumor‐draining regional lymph nodes in breast cancer
Authors: Yilmaz Izel , Tavukcuoglu Ece , Horzum Utku , Yilmaz Kerim Bora , Akinci Melih , Gulcelik Mehmet Ali , Oral Haluk Barbaros , Esendagli Gunes
Published: December 2023

Background

Functional status of T cells determines the responsiveness of cancer patients to immunotherapeutic interventions. Even though T cell‐mediated immunity is inaugurated in the tumor‐adjacent lymph nodes, peripheral blood has been routinely sampled for testing the immunological assays. The purpose of this study is to determine the immune checkpoint molecule expression and the exhaustion‐related phenotype of cytotoxic T cells in the regional lymph nodes from breast cancer patients.

Patients and methods

Multicolor immunophenotyping was used to determine the expression of PD‐1, TIM‐3, LAG3, CTLA‐4, CCR7, CD45RO, CD127, CD25, CXCR5, and ICOS molecules on CD3+CD4−CD56−CD8+ cytotoxic T cells freshly obtained from the lymph nodes and the peripheral blood samples of the breast cancer patients. The results were assessed together with the clinical data.

Results

A population of cytotoxic T cells was noted with high PD‐1 and CXCR5 expression in the lymph nodes of the breast cancer patients. Co‐expression of PD‐1, CXCR5, TIM‐3, and ICOS indicated a follicular helper T cell (Tfh)‐like, exhaustion‐related immunophenotype in these cytotoxic T cells. Only a minor population with CTLA‐4 and LAG3 expression was noted. The PD‐1+CXCR5+ cytotoxic T cells largely displayed CD45RO+CCR7+ central memory markers. The amount of CXCR5‐expressing PD‐1− cytotoxic T cells was elevated in the lymph nodes of the patients.

Conclusion

The regional lymph nodes of breast cancer patients harbor Tfh‐like exhausted cytotoxic T lymphocytes with high PD‐1 and TIM‐3 checkpoint molecule expression. The immunological conditions in the regional lymph nodes should be implicated for immune checkpoint immunotherapy (ICI) of cancer.
The more diverse the better: Identifying with a diverse neighbourhood mother community predicts greater intergroup contact
Authors: Riikonen Reetta , Finell Eerika , Seppälä Tuija , Stevenson Clifford
Published: December 2023

Although it has been shown that identification with a neighbourhood community can support intergroup relations within the community by providing resources to cope with intergroup contact, previous research has not investigated how the perceived diversity of the neighbourhood identity influences this process. This study extends research on neighbourhood identification by focusing on a specific group (mothers of small children), examining how and when identification with other mothers living in the same neighbourhood is related to intergroup contact with local outgroup mothers. We examined this in a survey study, for which we collected data from both Finnish majority and immigrant mothers at public maternal and child healthcare centres (N = 733). Our study showed that identification with the neighbourhood mother community was positively associated with intergroup contact, partly via perceived social support from other neighbourhood mothers for both Finnish majority and immigrant mothers. Our study additionally revealed that the perceived proportion of outgroup mothers in the local mother community moderated the relationship between identification and intergroup contact for both groups. Our findings highlight the significance of considering perceived diversity for determining when identification will support intergroup contact. Please refer to the Supplementary Material section to find this article's Community and Social Impact Statement.
Understanding the consumer's luxury webrooming intention: Moderating role of perceived risk and review
Authors: Akram Umair , Lavuri Rambabu
Published: December 2023

This research aims to examine luxury shoppers' webrooming intention, mediating (utilitarian value and hedonic value), and moderating (online perceived risk and reviews) effects. We used the stimulus‐organism‐response theory to provide a solid and holistic understanding of the concept. We collected 431 original survey data from Indian luxury shoppers who recently purchased luxury products and used structural equation modeling for data analysis. Results show that consumer traits (need for interaction and need for touch) had a positive impact on the perceived values (hedonic and utilitarian value) and webrooming intention. Channel‐related factors such as perceived ease of use had a direct impact on the hedonic value, while perceived usefulness had a direct impact on utilitarian value. Perceived values (hedonic and utilitarian values) positively mediated the channel and consumer traits factors and webrooming intent. Online perceived risk and reviews significantly moderated the relationship between perceived value and webrooming intent. This study adds to the knowledge of luxury marketing by analyzing webrooming and channel flipping.
Bottom‐Up Construction of Ni(II)‐Incorporated Covalent Organic Framework for Metallaphotoredox Catalysis
Authors: Hu Hai‐Chao , Wang Zhi‐Peng , Liang Lin , Du Xin‐Yu , Li Ting , Feng Jie , Xiao Tian‐Tian , Jin Ze‐Ming , Ding San‐Yuan , Liu Qiang , Lu Liang‐Qiu , Xiao Wen‐Jing , Wang Wei
Published: December 2023

The construction of an all‐in‐one catalyst, in which the photosensitizer and the transition metal site are close to each other, is important for improving the efficiency of metallaphotoredox catalysis. However, the development of convenient synthetic strategies for the precise construction of an all‐in‐one catalyst remains a challenging task due to the requirement of precise installation of the catalytic sites. Herein, we have successfully established a facile bottom‐up strategy for the direct synthesis of Ni(II)‐incorporated covalent organic framework (COF), named LZU‐713@Ni, as a versatile all‐in‐one metallaphotoredox catalyst. LZU‐713@Ni showed excellent activity and recyclability in the photoredox/nickel‐catalyzed C−O, C−S, and C−P cross‐coupling reactions. Notably, this catalyst displayed a better catalytic activity than its homogeneous analogues, physically mixed dual catalyst system, and, especially, LZU‐713/Ni which was prepared through post‐synthetic modification. The improved catalytic efficiency of LZU‐713@Ni should be attributed to the implementation of bottom‐up strategy, which incorporated the fixed, ordered, and abundant catalytic sites into its framework. This work sheds new light on the exploration of concise and effective strategies for the construction of multifunctional COF‐based photocatalysts.
Ca(II) and Yb(II) complexes featuring M(C≡C)4 structural motif: enforced proximity or genuine η2‐bonding?
Authors: Lyubov Dmitry M. , Zakaria Hamza , Nelyubina Yulia V. , Aysin Rinat R. , Bukalov Sergey S. , Trifonov Alexander A.
Published: December 2023

Bis(carbazolide) complexes M[3,6‐tBu2‐1,8‐(RC≡C)2Carb]2(THF)n (R=SiMe3, n=0, M=Ca, Yb; R=Ph, n=1, M=Ca, Yb; n=0, M=Yb) were synthesized through transamination reaction of M[N(SiMe3)2]2(THF)2 with two molar equivalents of carbazoles. The complexes feature M(η2‐C≡C)4 structural motif composed of M(II) ions encapsulated by four acetylene fragments due to atypical for alkaline‐ and rare‐earth metals η2‐interactions with triple C≡C bond. This interaction is evidenced experimentally by X‐ray diffraction, Raman spectroscopy in the solid state and by NMR‐spectroscopy in the solution. According to QTAIM analysis there are 4 bond critical points (3;−1) between the metal atom and each of the triple bonds, which are connected by a strongly curved, almost T‐shaped bond pathway.
Palladium Complexes with N,O‐Bidentate Ligands Based on N‐Oxide Units from Cyclic Secondary Amines: Synthesis and Catalytic Application in Mizoroki‐Heck Reaction
Authors: Jia Xuefeng , Wen Yanyan , He Changhui , Huang Xianqiang
Published: December 2023

Comprehensive Summary

Palladium‐catalyzed Mizoroki‐Heck reaction is a powerful and efficient method for construction of Csp2–Csp2 bonds. Herein, four palladium complexes (I—IV) with N,O‐bidentate ligands (L1—L4) based on N‐oxide units from cyclic secondary amines were easily synthesized and successfully applied in Mizoroki‐Heck reaction of aryl bromides with electron‐deficient olefins. X‐ray diffraction analyses indicated the palladium(II) atom of II took the distorted square planar geometry and was four‐coordinated by nitrogen and oxygen atoms from two ligands (L2). Two free chloride ions were presented as counter anions in complex II. But the palladium(II) center of IV was coordinated by nitrogen and oxygen atoms from one ligand (L4) as well as two chlorine atoms, which exhibited the nearly square‐planar geometry. The study on catalytic properties of palladium complexes revealed that complex II exhibited high activity superior to the other complexes. The coupling reactions of a series of aryl bromides and olefin derivatives proceeded in the presence of 2—5 mol% palladium complex II, giving the desired products in good to excellent yields. The advantages of this method such as good compatibility of functional groups, high yields, and short reaction times made it more attractive for constructing Csp2–Csp2 bonds in the synthesis of functional molecules and materials.
Femoral vessel complications after transfemoral TAVR—A contemporary sonography‐based assessment of 480 patients with third‐generation transcatheter valves
Authors: Werner Paul , Winter Martin , Müller Markus , Zierfuss Bernhard , Coti luliana , Mach Markus , Scherzer Sabine , Simon Paul , Laufer Günther , Willfort‐Ehringer Andrea , Andreas Martin
Published: December 2023

Background

Postinterventional sonographic assessment of the femoral artery after transfemoral transcatheter aortic valve replacement (TF‐TAVR) has the potential to identify several pathologies. We investigated the incidence and risk factors of femoral vessel complications in a modern TAVR collective using postinterventional sonography.

Methods

Between September 2017 and March 2022, 480 patients underwent TF‐TAVR with postinterventional femoral sonography at a single center. Clinical outcomes and adverse events were analyzed after the Valve Academic Research Consortium 3 (VARC‐3) criteria.

Results

In this cohort (51.2% male; age 80 ± 7.5 years, median EuroSCORE II 3.7) 74.8% (n = 359) were implanted with a self‐expandable and 25.2% (n = 121) with a balloon‐expandable valve. The main access (valve‐delivery) was located right in 91.4% (n = 438), and the primary closure system was Proglide in 95% (n = 456). Vascular complications (VC) were observed in 29.16% (n = 140) of patients; 23.3% (n = 112) presented with minor‐ and 5.8% (n = 28) with major VC. Postinterventional femoral artery stenosis on the main access was observed in 9.8% (n = 47). Multivariable logistic regression analysis revealed female sex (p = .03, odds ratio [OR] 2.32, 95% confidence interval [CI] 1.09–4.89) and the number of used endovascular closure devices (p = .014, OR 0.11, 95%CI 0.02–0.64) as predictive factors for femoral artery stenosis.

Conclusions

The incidence of postinterventional femoral artery stenosis following TF‐TAVR was higher than expected with a number of used closure devices and female sex being independent risk factors. Considering the continuous advance of TAVR in low‐risk patients with preserved physical activity, emphasis should be directed at the correct diagnosis and follow‐up of these complications.
Quantitative Systems Toxicology Modeling Informed Safe Dose Selection of Emvododstat in Acute Myeloid Leukemia Patients
Authors: Yang Kyunghee , Kong Ronald , Spiegel Robert , Baird John D. , O'Keefe Kylie , Howell Brett A. , Watkins Paul B.
Published: December 2023

Clinical investigation of emvododstat for the treatment of solid tumors was halted after two patients who were heavily treated with other anticancer therapies experienced drug‐induced liver failure. However, preclinical investigations supported that emvododstat at lower doses might be effective in treating acute myeloid leukemia (AML) and against severe acute respiratory syndrome‐coronavirus 2 as a dihydroorotate dehydrogenase inhibitor. Therefore, a quantitative systems toxicology model, DILIsym, was used to predict liver safety of the proposed dosing of emvododstat in AML clinical trials. In vitro mechanistic toxicity data of emvododstat and its desmethyl metabolite were integrated with in vivo exposure within DILIsym to predict hepatotoxicity responses in a simulated human population. DILIsym simulations predicted alanine aminotransferase elevations observed in prior emvododstat clinical trials in patients with solid tumors, but not in the prospective AML clinical trial with the proposed dosing regimens. Exposure predictions based on physiologically‐based pharmacokinetic modeling suggested that reduced doses of emvododstat would produce clinical exposures that would be efficacious to treat AML. In the AML clinical trial, only eight patients experienced aminotransferase elevations, all of which were mild (grade 1), all resolving within a short period of time, and no patient showed symptoms of hepatotoxicity, confirming the prospective prediction of liver safety. Overall, retrospective DILIsym simulations adequately predicted the liver safety liabilities of emvododstat in solid tumor trials and prospective simulations predicted the liver safety of reduced doses in an AML clinical trial. The modeling was critical to enabling regulatory approval to proceed with the AML clinical trial wherein the predicted liver safety was confirmed.
The role of risk management committee on the relationship between corporate carbon emission disclosure and capital structure
Authors: Ardianto Ardianto , Anridho Nadia , Cahyono Suham , Noman Alam Abu Hanifah Md. , Harymawan Iman
Published: December 2023

This study aims to examine the association between carbon emission disclosure and corporate capital structure, moderated by the presence of a risk management committee. Specifically, we aim to explore whether the existence of a risk management committee can mitigate the risks faced by companies when formulating capital structure strategies. We use data from non‐financial companies listed in the Carbon Disclosure Project (CDP) from 2015 to 2021 that disclose information on carbon emissions. To test our hypotheses, we employ fixed‐effects regression with standard error estimates. Our findings provide evidence that carbon emission disclosure is positively related to corporate capital structure, and that the moderating effect of the risk management committee is also positively associated with carbon emission disclosure and corporate capital structure. In addition, we conduct robustness and endogeneity tests, including Heckman (1979) two‐stage least squares, entropy balancing, propensity score matching, and two‐step GMM using Arellano‐Bond estimation. Furthermore, our study includes a batterary of cross‐sectional tests to rigorous the main findings. Finally, our study contributes to the literature on sustainable strategies and sustainable financing at the corporate level.
The impact of service experience on sustainable customer engagement: The mediation of green perceived value and customer satisfaction
Authors: Yan Dongwei , Wang Chenke , Sun Tianyi , Wen Decheng
Published: December 2023

With increasing public environmental awareness, accelerating green transformation has become inevitable for enterprises to achieve long‐term development. Sustainable customer engagement (sustainable CE) is a core concept of consumer participation in sustainable consumption. Based on partial least squares‐structural equation modeling, this study establishes a prediction model for sustainable CE and explores the impacts of service experience, green perceived value, and customer satisfaction on sustainable customer engagement. This study collected 682 valid data points from customers of green hotels and analyzed the relationships between sustainable CE and its antecedent variables. The results showed that peace of mind and product experience can directly promote sustainable customer engagement. Service experience can enhance sustainable CE through the serial mediation of green perceived value and customer satisfaction. The conclusions enrich the existing knowledge in the field of sustainable consumption and engagement marketing and provide effective suggestions for green hotel managers.
Acantholytic squamous cell carcinoma mimicking epithelioid angiosarcoma: A diagnostic challenge by cytology
Authors: Taweevisit Mana , Sutthiruangwong Piriya , Thorner Paul Scott
Published: December 2023

Squamous cell carcinoma (SCC) is the most common malignancy of the head and neck region. Most cases present little diagnostic difficulty on fine needle aspiration (FNA), but unusual variants can be problematic. The authors report a case of the acantholytic SCC of the oral cavity in a 36‐year‐old male. The FNA showed hypercellularity, with malignant cells arranged in isolation, loosely cohesive groups and a linear configuration. Such cells were round to elongated, with vesicular nuclei and prominent nucleoli. Cells possessed occasional intracytoplasmic vacuoles, misinterpreted on FNA to be vasoformative features as seen in malignant endothelial cells. The cytologic diagnosis was “positive for malignancy, suggestive of angiosarcoma”. A total excision was performed and by histology, the tumor was diagnosed as acantholytic SCC. The malignant cells were positive by immunostaining for AE1/AE3, p40, p63 and vimentin, but negative for CD31, CD34 and ERG. The intracytoplasmic vacuoles were PAS‐ and mucin‐negative and negative for the above antibodies. Testing for HPV (molecular and p16 immunostaining) was negative. This case highlights the diagnostic challenges on cytology when malignant acantholytic squamous cells show intracytoplasmic vacuoles, and stresses how immunohistochemistry is important for distinguishing acantholytic SCC from other mimics.
Subtypes of exercise are differentially associated with baseline eating disorder pathology and treatment outcome among individuals with bulimia nervosa
Authors: Lampe Elizabeth W. , Hill Naomi G. , Schleyer Brooke , Giannone Alyssa , Juarascio Adrienne S. , Manasse Stephanie M.
Published: December 2023

Objective

Individuals with bulimia nervosa (BN) engage in both maladaptive (i.e., compulsive and/or compensatory) and adaptive exercise (e.g., for enjoyment). No research has examined whether those who engage in adaptive, compulsive, and/or compensatory exercise exhibit differences in BN pathology or treatment outcome compared to those not engaging in exercise, limiting intervention efficacy.

Method

We examined associations of baseline exercise engagement with baseline and posttreatment BN pathology among 106 treatment‐seeking adults (Mage = 37.4, SDage = 12.95, 87.74% female, 68.87% White) enrolled across four clinical trials of outpatient enhanced cognitive behavioral therapy for BN (range: 12–16 sessions). Analysis of covariances examined associations between baseline exercise type and baseline/posttreatment global eating pathology, dietary restraint, loss‐of‐control (LOC) eating, and purging frequency.

Results

Those engaging in only adaptive exercise reported lower global eating pathology compared to those engaging in compulsive‐only exercise (Est = −1.493, p = .014, Mdiff = −.97) while those engaging in baseline compulsive exercise reported less LOC eating compared to those not engaging in exercise (Est = −22.42, p = .012, Mdiff = −12.50). Baseline engagement in compulsive‐only exercise was associated with lower posttreatment global eating pathology compared to baseline engagement in no exercise (Est = −.856, p = .023, Mdiff = −.64) and both compulsive and compensatory exercise (Est = .895, p = .026, Mdiff = −1.08).

Discussion

Those engaging in compulsive, compensatory, adaptive, and no exercise exhibit different patterns and severity of BN pathology. Future research is needed to position treatments to intervene on maladaptive, while still promoting adaptive, exercise.

Public significance statement

No research to date has examined whether those who engage in adaptive, compulsive, and/or compensatory exercise exhibit differences in BN pathology or treatment outcome compared to those not engaging in exercise, limiting targeted intervention efforts. We found that those engaging in compulsive, compensatory, and adaptive exercise exhibit different patterns of BN pathology and that adaptive exercise engagement was related to lower cognitive eating disorder symptoms at baseline.
Contrasting management regimes indicative of mesopredator release in temperate coastal fish assemblages
Authors: Synnes Ann‐Elin Wårøy , Olsen Esben Moland , Jorde Per Erik , Knutsen Halvor , Moland Even
Published: December 2023

The absence of functional top predators has been proposed as a mechanism acting to shape fish assemblages in temperate marine ecosystems, with cascading effects on lower trophic levels. We explore this scenario by comparing the trophic and functional status of fish assemblages in Norwegian marine national parks, open to fishing, to a nearby coastal seascape that harbors a system of marine protected areas (MPAs) including a no‐take zone. Demersal fish assemblages were sampled using fyke nets over three consecutive seasons. Atlantic cod (Gadus morhua) is potentially a dominant top predator in this ecosystem, and historically, this and other gadids have been targeted by the full range of former and present fisheries. In the present study, we find that average body size of the Atlantic cod was significantly larger in the zoned seascape compared to the unprotected areas (mean ± SD: 36.6 cm ± 14.38 vs. 23.4 ± 7.50; p < .001) and that the unprotected seascape was characterized by a higher abundance of mesopredator fish species. These observations are consistent with the hypothesis that the protection of top predators within MPAs aids to control the mesopredator populations and provides empirical support to the notion that the present state of many coastal fish assemblages is driven by mesopredator release linked to functional depletion of large top predators.
Effects of Hydrogen Addition, Oxygen Level, and Strain Rate on Combustion Characteristics of CH4/H2 in Staged MILD Combustion
Authors: Zhang Yanfei , Liu Dianlin , Huang Mingming , Liu Zhenxian , Li Qin , Zhang Haipeng , Hao Qing , Yu Zewen , Sha Haoxi
Published: December 2023

In this article, the effects of hydrogenation amount (0–80%), oxygen content (14–18%), and strain rate (10–1000 s−1) on the emission characteristics of NO and CO in moderate or intense low‐oxygen dilution (MILD) fractional combustion are studied under the actual working conditions of gas turbine (T = 723 K, P = 16.5 atm). The pathway of NO and CO production and the reaction with the greatest influence on their emissions are analyzed. In the findings, it is indicated that NO emissions are suppressed at lower hydrogen levels, while the addition of hydrogen leads to a decrease in CO emissions. Specifically, the key reaction for NO formation is H + NO + M = HNO + M, whereas CO emissions are primarily controlled by the direct reaction OH + CO = H + CO2. Furthermore, the reduction of oxygen levels effectively suppresses NO and CO emissions during MILD combustion. The variation in oxygen level exerts the greatest influence on the reaction rate of the NNH pathway. High concentrations of O2 are identified as the primary cause of elevated CO levels in MILD combustion. Finally, elevating the strain rate in MILD combustion demonstrates a mitigating effect on NO and CO emissions.
Solid oxide electrolysis stack development and upscaling
Authors: Di Iorio S. , Monnet T. , Palcoux G. , Ceruti L. , Mougin J.
Published: December 2023

Solid oxide electrolysis is considered an efficient technology to produce hydrogen. To deploy electrolysers at the GW scale, an increase in the individual component size (cells and stacks in particular) is required. The integration of larger cells (200 cm2 active area) into 25‐cell stacks has been successfully performed. Performances were in the range of –0.8 to –0.9 A cm−2 at 1.3 V at 700°C. The number of cells has also been increased to 50 and 75 cells. For this latter 75‐cell stack, the assembly of three 25‐cell substacks was considered. Good gastightness and high performances were achieved, although connections between substacks add a serial resistance that affects the stack total performances. Nevertheless, a current density of more than –0.8 A cm−2 was obtained at 1.3 V and 700°C, consistent with individual substack performances. Finally, a stack made of 50 200 cm2 cells has been assembled. Although a stack deformation was visible due to individual component thickness scattering, a good gastighness was achieved and a current density of –0.9 A cm−2 at 1.3 V and 700°C was measured. The low voltage scattering highlighted a good homogeneity of the fluidic distribution and of the electrical contacts within the stack.
One out of ten independent components shows flipped polarity with poorer data quality: EEG database study
Authors: Miyakoshi Makoto , Kim Hyeonseok , Nakanishi Masaki , Palmer Jason , Kanayama Noriaki
Published: December 2023

Independent component analysis (ICA) is widely used today for scalp‐recorded EEG analysis. One of the limitations of ICA‐based analysis is polarity indeterminacy. It is not easy to find detailed documentations that explains engineering solutions of how the polarity indeterminacy is addressed in a given implementation. We investigated how it is implemented in the case of EEGLAB and also the relation between the outcome of the polarity determination and classification of independent components (ICs) in terms of the estimated nature of the sources (brain, muscle, eye, etc.) using an open database of n = 212 EEG dataset of resting state recordings. We found that (1) about 91% of ICs showed positive‐dominant IC scalp topographies; (2) positive‐dominant ICs were more associated with brain‐originated signals; (3) positive‐dominant ICs showed more radial (peaked at 10–30 degrees deviations from the radial axis) dipolar projection pattern with less residual variance from fitting the equivalent current dipole. In conclusion, using the EEGLAB's default ICA algorithm, one out of 10 ICs results in flipping its polarity to negative, which is associated with non‐radial dipole orientation with higher residual variance. Thus, we determined EEGLAB biases toward positive polarity in decomposing high‐quality brain ICs.