bluuebunny/crossref_metadata_2025 huggingface dataset:
Metastatic pituitary neuroendocrine neoplasms: A case report of a malignant prolactinoma
Authors: Manique Inês , Amaral Sara , Rego Teresa , Coelho Andreia , Ponte Andreia , Brito Margarida , Palha Ana , Cortez Luísa , Forte Dalila , Sagarribay Amets , Cerqueira Luís , Pontinha Carlos , Mafra Manuela , Silva‐Nunes José
Published: April 2024

Key Clinical Message

We report a rare clinical case of a malignant prolactinoma in which the exponential increase of prolactin levels with minimal tumor growth and no response to treatment led to diagnosis of abdominal, thoracic, and vertebral metastases.
Bilateral intracochlear hemorrhage: A rare onset of chronic myelogenous leukemia
Authors: Flahat Babak , Bonnard Åsa , Arebro Julia
Published: April 2024

Key Clinical Message

Acute onset of vertigo and hearing loss is rare in leukemic disorders. MRI can diagnose intracochlear hemorrhage as the underlying cause. The hearing can improve but if severe hearing loss preserves, cochlear implantation can be considered.
Medication‐related osteonecrosis of the jaw: Case series and literature review
Authors: Kimathi Denis , Butt Fawzia , Guthua Symon , Waweru Wairimu
Published: April 2024

Key Clinical Message

Medication‐related osteonecrosis of the Jaw (MRONJ) is a rare complication of the jaws following the administration of antiresorptive or antiangiogenic drugs. This condition poses a major challenge to its management. Its prevention and management need a multidisciplinary collaboration. We described three patients with MRONJ including their presentation, investigations, management protocols, and outcomes. A brief appraisal of the literature on MRONJ was also done.

Medication‐related osteonecrosis of the jaw (MRONJ) is a rare complication of the jaws following the administration of antiresorptive or antiangiogenic drugs. This condition poses a major challenge to its management. We present an appraisal of the literature and three cases of MRONJ. An appraisal of 3 patients who presented to the oral and maxillofacial clinic with MRONJ was done. Relevant physical examination findings, radiological images, clinical photographs and follow‐up was documented. One patient had multiple myeloma while the other two had metastatic cancer. All had received zoledronic acid before developing MRONJ. One patient was surgically treated and successfully recovered while two were managed conservatively. Patients taking antiresorptive medications are at risk of developing MRONJ. Prevention and management of the condition calls for a multidisciplinary collaboration. Patients taking antiresorptive medications need good education on the risks associated with the medications and how to recognize early signs and symptoms.
Bilateral dens evaginatus and associated cystic pathology: An unusual case report
Authors: Lee Haeseong , Le Bach , Sedghizadeh Parish
Published: April 2024

Key Clinical Message

Dens evaginatus (DE) presents a clinical conundrum due to its fragility and propensity to cause pulpal and periapical complications. Clinicians should heed the presence of DE during clinical examinations and avoid unnecessary intervention.
Arrest of labor secondary to large uterine fibroid
Authors: Ruiz Jesus
Published: April 2024

Key Clinical Message

Large uterine fibroids during pregnancy are associated with increased maternal and fetal complications. Large uterine fibroids should be kept in mind as a cause for arrest of labor and the need for cesarean delivery.

Uterine fibroids >5 cm in diameter are more likely to grow during pregnancy and cause obstetrical complications. We report a case of a large 9 cm subserosal uterine fibroid as the cause for the arrest of labor and the need for cesarean delivery.
Aromaticity in Semi‐Condensed Figure‐Eight Molecules
Authors: Artigas Albert , Carissan Yannick , Hagebaum‐Reignier Denis , Bock Harald , Durola Fabien , Coquerel Yoann
Published: April 2024

Electron delocalization and aromaticity was comparatively evaluated in recently synthesized figure‐eight molecules made of two condensed U‐shaped polycyclic aromatic hydrocarbon moieties connected either by two single bonds or by two para‐phenylene groups. The selected examples include molecules that incorporate eight‐membered and sixteen‐membered rings, as well as a doubly [5]helicene‐bridged (1,4)cyclophane. We probe whether some electron delocalization could occur through the stereogenic single bonds in these molecules: Is aromaticity purely (semi‐)local, or possibly also global in these molecules? It was concluded that the situation can go from a purely (semi‐)local character when the dihedral angle at the connecting single bonds is large, such as in biphenyl, to a predominantly (semi‐)local character with a minor global contribution when the dihedral angle is small, such as in the para‐phenylene connectors of the [5] helicene‐bridged cyclophane.
A Bis‐Porphyrin Cavitand Breathing‐In to Constrict Bucky Balls
Authors: Kumari Anupam , Kumar Mondal Pradip , Verma Preetika , Mahato Paritosh , S Sujesh , Mandal Koushik , Polentarutti Maurizio , Lakshmanna Yapamanu Adithya , Sankar Jeyaraman
Published: April 2024

Bis‐porphyrin cages have long been exploited to bind fullerenes selectively for various applications. The major consideration for an effective binding here had been the cavity size. Herein, we structurally demonstrate that a bis‐Ni−porphyrin cavitand having even a smaller cavity can host a larger fullerene by a breathing and ruffling mechanism. It has also been shown that both the electronic and steric influence at the meso‐ positions of the porphyrin in fact dictate the binding character. The smaller cavity of 2NiD exhibits preferential binding for C70 over C60; however, surprisingly, the larger cavities in 2HD and 2NiTD display stronger affinities for C60 over the larger fullerene. We show here that the structural elasticity infused both by the metalloporphyrins and the connecting bridges play a major role in directing the binding. These conclusions have adequately been supported by structural and spectroscopic investigations. Additionally, the suitability of one of the conjugates for photoinduced charge‐separation has been investigated using ultrafast transient absorption measurements. 2NiD⊃C60 has a charge separation timescale of ~0.8 ps, while charge recombination occurs at a longer timescale of ~920 ps.
Alared: Solvatochromic and Fluorogenic Red Amino Acid for Ratiometric Live‐Cell Imaging of Bioactive Peptides
Authors: Mirloup Antoine , Berthomé Yann , Riché Stéphanie , Wagner Patrick , Hanser Fabien , Laurent Arthur , Iturrioz Xavier , Llorens‐Cortes Catherine , Karpenko Julie , Bonnet Dominique
Published: April 2024

To fill the need for environmentally sensitive fluorescent unnatural amino acids able to operate in the red region of the spectrum, we have designed and synthesized Alared, a red solvatochromic and fluorogenic amino acid derived from the Nile Red chromophore. The new unnatural amino acid can be easily integrated into bioactive peptides using classical solid‐phase peptide synthesis. The fluorescence quantum yield and the emission maximum of Alared‐labeled peptides vary in a broad range depending on the peptide's environment, making Alared a powerful reporter of biomolecular interactions. Due to its red‐shifted absorption and emission spectra, Alared‐labeled peptides could be followed in living cells with minimal interference from cellular autofluorescence. Using ratiometric fluorescence microscopy, we were able to track the fate of the Alared‐labeled peptide agonists of the apelin G protein‐coupled receptor upon receptor activation and internalization. Due to its color‐shifting environmentally sensitive emission, Alared allowed for distinguishing the fractions of peptides that are specifically bound to the receptor or unspecifically bound to different cellular membranes.
Prediction of Bond Dissociation Energy for Organic Molecules Based on a Machine‐Learning Approach
Authors: Liu Yidi , Li Yao , Yang Qi , Yang Jin‐Dong , Zhang Long , Luo Sanzhong
Published: April 2024

Comprehensive Summary

Bond dissociation energy (BDE), which refers to the enthalpy change for the homolysis of a specific covalent bond, is one of the basic thermodynamic properties of molecules. It is very important for understanding chemical reactivities, chemical properties and chemical transformations. Here, a machine learning‐based comprehensive BDE prediction model was established based on the iBonD experimental BDE dataset and the calculated BDE dataset by St. John et al. Differential Structural and PhysicOChemical (D‐SPOC) descriptors that reflected changes in molecules’ structural and physicochemical features in the process of bond homolysis were designed as input features. The model trained with LightGBM algorithm gave a low mean absolute error (MAE) of 1.03 kcal/mol on the test set. The D‐SPOC model could apply to accurate BDE prediction of phenol O—H bonds, uncommon N‐SCF3 and O‐SCF3 reagents, and β‐C—H bonds in enamine intermediates. A fast online prediction platform was constructed based on the D‐SPOC model, which could be found at http://isyn.luoszgroup.com/bde_prediction.
A Selenium Atom Involved Covalent Organic Framework for Window Ledge Photocatalytic Oxidation of Sulfides
Authors: Yang Fan , Li Xia , Qu Hong‐Yan , Kan Jing‐Lan , Guo Yuan , Dong Yu‐Bin
Published: April 2024

Comprehensive Summary

Covalent organic frameworks (COFs) driven photocatalytic organic transformations especially photooxidation reactions have become a fertile topic and attracted numerous research attentions. Boosting the charge generation and transport process is the key factor for achieving high catalytic efficiencies. As one of the most effective strategies, the introduction of “heavy atoms” into the long‐range ordered conjugated backbones can effectively facilitate the intersystem crossing (ISC) process and hence improve the generation of active oxygens, which is beneficial for the oxidation. In this work, we designed and synthesized a benzoselenadiazole based covalent organic framework (COF) material, BSe‐COF with heavy atom of selenium (Se), and a benzothiadiazole based BT‐COF with isomorphic backbone for comparison. Compared to BT‐COF, BSe‐COF exhibits broader absorption range, stronger photocurrent response and enhanced intersystem crossing (ISC) with higher singlet oxygen (1O2) generation efficiency. When applied in photocatalytic organic transformation, BSe‐COF presents remarkably higher photocatalytic activity in the oxidation of sulfides than BT‐COF under the irradiation of blue LED lamp. Furthermore, BSe‐COF can be used as efficient photocatalyst for the window ledge reaction with high yields (over 84%) of various sulfoxides from a wide range of thioether substrates scope.
Catalytic Asymmetric Synthesis of Inherently Chiral Saddle‐Shaped Dibenzo[b,f][1,5]diazocines†
Authors: Zhou Jinmiao , Tang Mengyao , Yang Xiaoyu
Published: April 2024

Comprehensive Summary

Dibenzo[b,f][1,5]diazocines are a class of eight‐membered heterocycles, which exhibit unique rigid saddle‐shaped structure and possess inherent chirality. In this study, we report a convenient and straightforward method for the catalytic enantioselective synthesis of these unique chiral molecules through chiral phosphoric acid‐catalyzed dimerization of 2‐acylbenzoisocyanates. Notably, the addition of corresponding 2‐acylaniline as the co‐catalyst significantly improved the efficiency of these reactions, and a simple phase separation operation resulted in products with excellent enantiopurity. Experimental studies were performed to elucidate the mechanism behind these reactions, leading to the proposal of a plausible reaction mechanism based on the study findings.
Exploring Raloxifene‐Based Metallodrugs: A Versatile Vector Combined with Platinum(II), Palladium(II) and Nickel(II) Dichlorides and Carborates against Triple‐Negative Breast Cancer
Authors: Kazimir Aleksandr , Götze Tom , Lönnecke Peter , Murganić Blagoje , Mijatović Sanja , Maksimović‐Ivanić Danijela , Hey‐Hawkins Evamarie
Published: April 2024

Triple‐negative breast cancer (TNBC) poses challenges in therapy due to the absence of target expression such as estrogen receptor (ER), progesterone receptor (PR), and human epidermal growth factor receptor 2 (HER2). Frequently, the treatment of TNBC involves the combination of several therapeutics. However, an enhanced therapeutic effect can be also achieved within a single molecule. The efficacy of raloxifene can be improved by designing a raloxifene‐based hybrid drug bearing a 2,2’‐bipyridine moiety (2). Integration of platinum(II), palladium(II), and nickel(II) complexes into this structure dramatically changed the cytotoxicity. The platinum(II) dichloride complex 3 did not demonstrate any activity, while palladium(II) and nickel(II) dichloride complexes 4 and 5 exhibited various cytotoxic behavior towards different types of hormone‐receptor positive (HR+) cancer and TNBC cell lines. The replacement of the two chlorido ligands in 3–5 with a dicarbollide (carborate) ion [C2B9H11]2− resulted in reduced activity of compounds 6, 7, and 8. However, the palladacarborane complex 7 demonstrated higher selectivity towards TNBC. Furthermore, the mechanism of action was shifted from cytotoxic to explicitly cytostatic with detectable proliferation arrest and accelerated aging, characterized by senescence‐associated phenotype of TNBC cells. This study provides valuable insights into the development of hybrid therapeutics against TNBC.
Safety and efficacy of percutaneous image‐guided ablation for soft tissue sarcoma metastases to the liver
Authors: Awad Ahmed , Pal Koustav , Yevich Steven , Kuban Joshua D. , Tam Alda , Odisio Bruno C. , Gupta Sanjay , Habibollahi Peiman , Bishop Andrew J. , Conley Anthony Paul , Somaiah Neeta , Araujo Dejka M. , Zarzour Maria Alejandra , Ratan Ravin , Roland Christina L. , Keung Emily Z. , Huang Steven Y. , Sheth Rahul A.
Published: April 2024

Purpose

To evaluate outcomes following percutaneous image‐guided ablation of soft tissue sarcoma metastases to the liver.

Materials and Methods

A single‐institution retrospective analysis of patients with a diagnosis of metastatic soft tissue sarcoma who underwent percutaneous image‐guided ablation of hepatic metastases between January 2011 and December 2021 was performed. Patients with less than 60 days of follow‐up after ablation were excluded. The primary outcome was local tumor progression‐free survival (LPFS). Secondary outcomes included overall survival, liver‐specific progression‐free survival. and chemotherapy‐free survival.

Results

Fifty‐five patients who underwent percutaneous ablation for 84 metastatic liver lesions were included. The most common histopathological subtypes were leiomyosarcoma (23/55), followed by gastrointestinal stromal tumor (22/55). The median treated liver lesions was 2 (range, 1–8), whereas the median size of metastases were 1.8 cm (0.3–8.7 cm). Complete response at 2 months was achieved in 90.5% of the treated lesions. LPFS was 83% at 1 year and 80% at 2 years. Liver‐specific progression‐free survival was 66% at 1 year and 40% at 2 years. The overall survival at 1 and 2 years was 98% and 94%. The chemotherapy‐free holiday from the start of ablation was 71.2% at 12 months. The complication rate was 3.6% (2/55); one of the complications was Common Terminology Criteria for Adverse Events grade 3 or higher. LPFS subgroup analysis for leiomyosarcoma versus gastrointestinal stromal tumor suggests histology‐agnostic outcomes (2 years, 89% vs 82%, p = .35).

Conclusion

Percutaneous image‐guided liver ablation of soft tissue sarcoma metastases is safe and efficacious.
The impact of outpatient supportive oncology on cancer care cost and utilization
Authors: Worster Brooke , Zhu Yifan , Garber Gregory , Kieffer Sawyer , Smith‐McLallen Aaron
Published: April 2024

Background

Supportive oncology (SO) care reduces symptom severity, admissions, and costs in patients with advanced cancer. This study examines the impact of SO care on utilization and costs.

Methods

Retrospective analysis of utilization and costs comparing patients enrolled in SO versus three comparison cohorts who did not receive SO. Using claims, the authors estimated differences in health care utilization and cost between the treatment group and comparison cohorts. The treatment group consisting of patients treated for cancer at an National Cancer Institute‐designated cancer center who received SO between January 2018 and December 2019 were compared to an asynchronous cohort that received cancer care before January 2018 (n = 60), a contemporaneous cohort with palliative care receiving SO care from other providers in the Southeastern Pennsylvania region during the program period (n = 86), and a contemporaneous cohort without palliative care consisting of patients at other cancer centers who were eligible for but did not receive SO care (n = 393).

Results

At 30, 60, and 90 days post‐enrollment into SO, the treatment group had between 27% and 70% fewer inpatient admissions and between 16% and 54% fewer emergency department visits (p < .05) compared to non‐SO cohorts. At 90 days following enrollment in SO care, total medical costs were between 4.4% and 24.5% lower for the treatment group across all comparisons (p < .05).

Conclusions

SO is associated with reduced admissions, emergency department visits, and total costs in advanced cancer patients. Developing innovative reimbursement models could be a cost‐effective approach to improve care of patients with advanced cancer.
The Effectiveness of Silver and Gold in Catalytic Homogenous and Heterogenous Borohydride Hydrolysis – a DFT Study
Authors: Raju Karimadom Basil , Kornweitz Haya
Published: April 2024

Energy demands, and environmental aspects raised the need to study hydrogen‐carrying material such as borohydride for the practical usage of hydrogen as a cleaner and more efficient fuel. A proper understanding of the hydrogen generation mechanism is a key requirement for the designing of efficient catalysts, as the non‐catalytic hydrolysis of borohydride in non‐acidic media is a slow process. The hydrolysis mechanism of borohydride varies considerably using homogeneous and heterogeneous catalysts. A comparison of the hydrolysis mechanism of borohydride using gold and silver as homogenous and heterogeneous catalysts is given in this review. Unexpectedly, with gold catalyst, Au+ or Au(111), only two steps of hydrolysis occur and BH(OH)2 is produced, while with silver catalyst, Ag+ or Ag(111), the hydrolysis can proceed to completion.
Combining text analytics and network path extraction to trace CSR in the social sciences: Intellectual structures and diffusion trajectories
Authors: Yu Dejian , Xiang Bo , Pan Zhuoya
Published: April 2024

Corporate social responsibility (CSR) has evolved over time into a mature interdisciplinary scientific field. However, there is a lack of research to explore the disciplinary association patterns and diffusion trajectories of scientific knowledge within this field. This research proposes a knowledge tracing framework that combines text analysis based on scientific texts and main path extraction based on citation networks to fill this gap. This framework is implemented in a dataset containing 15,949 papers related to CSR in the social sciences published from 1969 to 2022. This study identifies 19 main research directions within this field and their five growth trends. Combined with disciplinary categories of publication venues, both the disciplinary origins and disciplinary association patterns of these knowledge contents are also revealed. Besides that, three knowledge diffusion paths are obtained, which meticulously reveal the knowledge evolution and paradigm shift. Aside from the methodological novelty and result scarcity, this study also identifies research streams and potential opportunities. To begin with, CSR‐related studies have shown the tendency of microscopic and interdisciplinary. Then, related research methods show the tendency to be complicated and focus on causal logic. On this basis, some future agendas of CSR are also proposed in this work.
Effect of the Brazilian corporate sustainability index on cash holdings and the moderating role of Covid‐19
Authors: dos Santos Cunha Lucelma Maria , Azevedo Yuri Gomes Paiva , Figueira Laís Manfiolli , de Souza Ribeiro Maisa
Published: April 2024

This study investigates the effect of the Brazilian Corporate Sustainability Index (ISE) on cash holdings and the moderating role of Covid‐19. Our sample comprises 213 non‐financial publicly listed firms from Brazil with 1072 firm‐year observations available on Refinitiv Eikon database from 2015 to 2022. Our overall findings show a positive association between ISE and cash holdings for the entire period analyzed. However, we find that ISE companies retained less cash in the pandemic period. Furthermore, external financial constraint is a channel through which ISE companies tend to lower their levels of cash holdings during the Covid‐19 outbreak. Our main results are robust to alternative measures of cash holdings. Therefore, we contribute to the corporate financial, sustainability, and Covid‐19 literature by providing the first empirical evidence of the dynamic nature of the relationship between ISE and cash holdings during external shocks and further comprehension to investors that sustainable practices reflected on the financial resource strategies are essential information during crises.
Commutation strategy for reduced output voltage ripple in alternative cascaded boost converter
Authors: García‐Vite Pedro Martín , Rebullosa‐Castillo Josué Francisco , García‐Perales Manuel Alejandro , Reyes‐García Brenda Lizeth , García‐Guendulain Crescencio
Published: April 2024

With the rapid penetration of low‐voltage direct current (DC) generators such as photovoltaic panels and storage energy systems, the need for processing energy has propitiated the optimization of power electronics converters. Conventional topologies of power electronics converters have well‐known limitations, mainly due to the parasitic elements and finite commutation times, which do not allow for obtaining a sufficient voltage gain. The literature review has demonstrated that cascade topologies are suited to overcome these limitations. However, to provide a low‐ripple output voltage, they require high values of capacitances. This paper presents an alternative boost converter developed by cascading two power cells. The conventional configuration is slightly modified, producing an alternative power cell. Even though the number of elements is increased, following the suggested commutation strategy, the derived converter can substantially reduce the output voltage ripple. Therefore, capacitors of small value can be employed, avoiding using electrolytic capacitors with shorter life spans than their film counterparts. Besides, given the cascaded connection, the converter possesses a quadratic‐type gain since two independent commanding signals are applied. The different states of commutation are analyzed in depth, allowing the selection of an adequate commutation strategy, which gives the advantage of canceling the output voltage ripple. The mathematical model of the converter is presented and then validated via a scale‐lab prototype. The simulation results evidence the good dynamic performance of the control‐loop design by means of the frequency response analysis.
T‐RESIN: Throughput‐aware dynamic resource orchestration for Internet of Everything‐enabled software‐defined edge networks
Authors: Agrawal Lalita , Mondal Ayan , Obaidat Mohammad S.
Published: April 2024

In this work, we address the problem of resource allocation in Internet of Everything (IoE)‐enabled software‐defined edge networks. In the existing literature, the researchers considered optimizing the performance of the software‐defined networking (SDN) platform using a single‐tier architecture, where the Internet of Things (IoT) devices are in the same tier. However, with the advent of edge computing, we can explore the two‐tier architecture of edge networks—local tier and edge tier—in the presence of SDN, which has not been explored. Hence, we propose an evolutionary game‐based resource allocation scheme for software‐defined edge networks. Additionally, we aim to optimize the QoS of the edge‐based IoE services while optimizing the throughput of the system. The IoT devices use the proposed scheme in the local tier to identify the optimized mapping to the SDN switches. On the other hand, in the edge tier, the proposed scheme aims to optimize the throughput while allocating the IoE service to the optimal subset of edge devices. We evaluated the performance of the proposed scheme using the Python3‐based Mininet platform in the presence of Ryu Controller and Open vSwitches. Ryu is an element‐based software defined networking framework, which offers software elements with well‐described API that enables developers to produce new network control functions. We observed that by using T‐RESIN, the network throughput increases by 27.98%–31.84% than using the existing schemes.
Cytopathology fellowship match: Pros and cons
Authors: Wu Roseann I. , Torous Vanda F.
Published: April 2024

A cytopathology fellowship match would create an enforced and structured recruitment timeline for the benefit of applicants and programs. Major benefits would include delaying fellowship applications to allow residents to explore different subspecialty areas, a standardized application process for administrative ease, and optimization of matches between applicants and programs based on ranked preferences rather than use of time‐limited “exploding offers.” The overall gains in efficiency and achieving the primary goals of supporting trainees and recruiting in an equitable and inclusive manner outweigh any downsides to instituting a cytopathology fellowship match. We aim to review the major discussions around this ongoing debate, arriving at the same conclusion as others in the literature that a pan‐pathology fellowship match is ideal and that leadership from the Association of Pathology Chairs will be essential in unifying the fractured fellowship recruitment process.
Embedding Perovskite in Polymer Matrix Achieved Positive Temperature Response with Inversed Temperature Crystallization
Authors: Peng Meiting , Guan Xue , Wu Yingzhu , Zhang Nan , Feng Qi , Tian Liyong , Wu Yancheng , Zhang Yangfan , Gan Feng , Deng Fuqin , Huang Meilin , Xing Guichuan , Yi Ningbo
Published: April 2024

Organic perovskites are promising semiconductor materials for advanced photoelectric applications. Their fluorescence typically shows a negative temperature coefficient due to bandgap change and structural instability. In this study, a novel perovskite‐based composite with positive sensitivity to temperature was designed and obtained based on its inverse temperature crystallization, demonstrating good flexibility and solution processability. The supercritical drying method was used to address the limitations of annealing drying in preparing high‐performance perovskite. Optimizing the precursor composition proved to be an effective approach for achieving high fluorescence and structural integrity in the perovskite material. This perovskite‐based composite exhibited a positive temperature sensitivity of 28.563% °C−1 for intensity change and excellent temperature cycling reversibility in the range of 25–40 °C in an ambient environment. This made it suitable for use as a smart window with rapid response. Furthermore, the perovskite composite was found to offer temperature‐sensing photoluminescence and flexible processability due to its components of perovskite‐based compounds and polyethylene oxide. The organic precursor solvent could be a promising candidate for use as ink to print or write on various substrates for optoelectronic devices responding to temperature.
Dependence of Initial Capacity Irreversibility on Oxygen Framework Chemistry in Li‐Rich Layered Cathode Oxides
Authors: Li Xiao , Zhang Yibin , Qiu Bao , Chen Guoxin , Zhou Yuhuan , Gu Qingwen , Liu Zhaoping
Published: April 2024

The undesirable capacity loss after first cycle is universal among layered cathode materials, which results in the capacity and energy decay. The key to resolving this obstacle lies in understanding the effect and origin of specific active Li sites during discharge process. In this study, focusing on Ah‐level pouch cells for reliability, an ultrahigh initial Coulombic efficiency (96.1%) is achieved in an archetypical Li‐rich layered oxide material. Combining the structure and electrochemistry analysis, we demonstrate that the achievement of high‐capacity reversibility is a kinetic effect, primarily related to the sluggish Li mobility during oxygen reduction. Activating oxygen reduction through small density would induce the oxygen framework contraction, which, according to Pauli repulsion, imposes a great repulsive force to hinder the transport of tetrahedral Li. The tetrahedral Li storage upon deep oxygen reduction is experimentally visualized and, more importantly, contributes to 6% Coulombic efficiency enhancement as well as 10% energy density improvement for pouch cells, which shows great potentials breaking through the capacity and energy limitation imposed by intercalation chemistry.
CuO/Co3O4 Bifunctional Catalysts for Electrocatalytic 5‐Hydroxymethylfurfural Oxidation Coupled Cathodic Ammonia Production
Authors: Zhang Li , Jin Peiyue , Wu Ze , Zhou Bo , Jiang Junchang , Deng Aomeng , Li Qiuyue , Hussain Tanveer , Zhang Yiqiong , Liu Hanwen , Wang Shuangyin
Published: April 2024

The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value‐added chemicals and nitrogen cycling. Herein, in this work, CuO/Co3O4 with heterogeneous interface is successfully constructed as a bifunctional catalyst for the electrooxidation of 5‐hydroxymethylfurfural to 2,5‐furandicarboxylic acid and the electroreduction of nitrate to ammonia (NH3). The open‐circuit potential spontaneous experiment shows that more 5‐hydroxymethylfurfural molecules are adsorbed in the Helmholtz layer of the CuO/Co3O4 composite, which certifies that the CuO/Co3O4 heterostructure is conducive to the kinetic adsorption of 5‐hydroxymethylfurfural. In situ electrochemical impedance spectroscopy further shows that CuO/Co3O4 has faster reaction kinetics and lower reaction potential in oxygen evolution reaction and 5‐hydroxymethylfurfural electrocatalytic oxidation. Moreover, CuO/Co3O4 also has a good reduction effect on . The ex‐situ Raman spectroscopy shows that under the reduction potential, the metal oxide is reduced, and the generated Cu2O can be used as a new active site for the reaction to promote the electrocatalytic conversion of to NH3 synthesis. This work provides valuable guidance for the synthesis of value‐added chemicals by 5‐hydroxymethylfurfural electrocatalytic oxidation coupled with while efficiently producing NH3.
Li‐Ion Transport Mechanisms in Selenide‐Based Solid‐State Electrolytes in Lithium‐Metal Batteries: A Study of Li8SeN2, Li7PSe6, and Li6PSe5X (X = Cl, Br, I)
Authors: Xiao Wenshan , Wu Mingwei , Wang Huan , Zhao Yan , He Qiu
Published: April 2024

To achieve high‐energy‐density and safe lithium‐metal batteries (LMBs), solid‐state electrolytes (SSEs) that exhibit fast Li‐ion conductivity and good stability against lithium metal are of great importance. This study presents a systematic exploration of selenide‐based materials as potential SSE candidates. Initially, Li8SeN2 and Li7PSe6 were selected from 25 ternary selenides based on their ability to form stable interfaces with lithium metal. Subsequently, their favorable electronic insulation and mechanical properties were verified. Furthermore, extensive theoretical investigations were conducted to elucidate the fundamental mechanisms underlying Li‐ion migration in Li8SeN2, Li7PSe6, and derived Li6PSe5X (X = Cl, Br, I). Notably, the highly favorable Li‐ion conduction mechanism of vacancy diffusion was identified in Li6PSe5Cl and Li7PSe6, which exhibited remarkably low activation energies of 0.21 and 0.23 eV, and conductivity values of 3.85 × 10−2 and 2.47 × 10−2 S cm−1 at 300 K, respectively. In contrast, Li‐ion migration in Li8SeN2 was found to occur via a substitution mechanism with a significant diffusion energy barrier, resulting in a high activation energy and low Li‐ion conductivity of 0.54 eV and 3.6 × 10−6 S cm−1, respectively. Throughout this study, it was found that the ab initio molecular dynamics and nudged elastic band methods are complementary in revealing the Li‐ion conduction mechanisms. Utilizing both methods proved to be efficient, as relying on only one of them would be insufficient. The discoveries made and methodology presented in this work lay a solid foundation and provide valuable insights for future research on SSEs for LMBs.
Prognostic value of growth differentiation factor‐15 in heart failure among whole ejection fraction phenotypes
Authors: Lyu Lyu , Xu Juan , Xv Cui , Xiao Hunan , Liu Zhenzhen , He Yanru , Gao Weiyang , Hao Benchuan , Liu Hongbin
Published: April 2024

Aims

The utility of growth differentiation factor‐15 (GDF‐15) in predicting long‐term adverse outcomes in heart failure (HF) patients is not well established. This study explored the relationship between GDF‐15 levels and adverse outcomes in HF patients across various ejection fraction (EF) phenotypes associated with coronary heart disease (CHD) and evaluated the added prognostic value of incorporating GDF‐15 into the Meta‐Analysis Global Group in Chronic Heart Failure (MAGGIC) risk score‐based model.

Methods and results

This single‐centre cohort study included 823 HF patients, categorized into 230 (27.9%) reduced EF (HFrEF), 271 (32.9%) mid‐range EF (HFmrEF), and 322 (39.1%) preserved EF (HFpEF) groups. The median age was 68.0 years (range: 56.0–77.0), and 245 (29.8%) were females. Compared with the HFrEF and HFmrEF groups, the HFpEF group had a higher GDF‐15 concentration (P = 0.002) and a higher MAGGIC risk score (P < 0.001). We examined the associations between GDF‐15 levels and the risks of all‐cause mortality and HF rehospitalization using Cox regression models. The C‐index, integrated discrimination improvement (IDI), and net reclassification improvement (NRI) metrics were employed to assess the incremental prognostic value. During the 9.4 year follow‐up period, 425 patients died, and 484 were rehospitalized due to HF. Multivariate Cox regression analysis revealed that elevated GDF‐15 levels were significantly associated with an increased risk of all‐cause mortality [hazard ratio (HR) = 1.36, 95% confidence interval (CI): 1.20–1.54; P < 0.001] and HF rehospitalization (HR = 1.75, 95% CI: 1.57–1.95; P < 0.001) across all HF phenotypes. This association remained significant when GDF‐15 was treated as a categorical variable (high GDF‐15 group: all‐cause death: HR = 1.73, 95% CI: 1.40–2.14; P < 0.001; HF rehospitalization: HR = 3.37, 95% CI: 2.73–4.15; P < 0.001). Inclusion of GDF‐15 in the MAGGIC risk score‐based model provided additional prognostic value for all HF patients (Δ C‐index = 0.021, 95% CI: 0.002–0.041; IDI = 0.011, 95% CI: 0.001–0.025; continuous NRI = 0.489, 95% CI: 0.174–0.629) and HF rehospitalization (Δ C‐index = 0.034, 95% CI: 0.005–0.063; IDI = 0.021, 95% CI: 0.007–0.032; continuous NRI = 0.307, 95% CI: 0.147–0.548), particularly in the HFpEF subgroup.

Conclusions

GDF‐15 is identified as an independent risk factor for adverse outcomes in HF patients across the entire EF spectrum in the context of CHD. Integrating GDF‐15 into the MAGGIC risk score‐based model enhances its prognostic capability for adverse outcomes in the general HF population. This incremental prognostic effect was observed specifically in the HFpEF subgroup and not in other subgroups.
Intense Photoluminescence and Mechanoluminescence of Novel BaLaAl3O7 : xEu3+ Red Nanophosphors
Authors: Li Chengren , Guo Chunlai , Wang Jianmin , Zhao Fei , Zhang Zhen , Zhao Qianyun , Cui Jinyi
Published: April 2024

A series of BaLaAl3O7 : xEu3+ nanophosphors have been prepared by the high‐temperature solid state reaction method. The XRD and SEM characterization results present that there exists a slight influence on the crystal structure and the average particle size of the nanophosphors while the Eu3+ ions are doped into the matrix. The intense and narrow red photoluminescence spectra have been measured under the ultraviolet excitation and there are two optimal Eu3+ concentrations of 0.8 and 12 mol %, respectively, and the intensity of the former is stronger than that of the latter. Furthermore, the mechanoluminescence phenomena with the same color are also observed when the samples are scratched with a pen. The calculated results based on the measurements of thermoluminescence spectra reveal that the total initial concentration of trapped carriers of BaLaAl3O7 : 12Eu3+ nanophosphors is larger than that of BaLaAl3O7 : 0.8Eu3+ sample, which causes the change trend of ML intensity to be opposite to that of PL intensity even though both have the same Eu3+ doping concentrations.
Transition‐Metal‐Free Carbonyl Reduction and Hydrodefluorination of β‐Trifluoromethyl Enones with Hydrosilanes: Synthesis of gem‐Difluorovinyl Alcohols
Authors: Zhang Peng‐Yuan , Hu Ya‐Fei , Chu Jia‐Hao , Zheng Ren‐Jun , Ma Mengtao , Shen Zhi‐Liang , Chu Xue‐Qiang
Published: April 2024

A tandem carbonyl reduction and hydrodefluorination of β‐trifluoromethyl enones with hydrosilanes under transition‐metal‐free conditions was developed for the synthesis of a variety of valuable gem‐difluorovinyl alcohols. The hydrosilane could act as both a reductive agent and a C(sp3)‐F bond‐breaking promoter under mild reaction conditions. Synthetically useful organofluorides, such as gem‐fluorophosphine alkene, gem‐difluorovinyl ketone, and fluorinated dihydrofuran derivatives could be readily constructed by further transformations of the obtained gem‐difluorovinyl alcohols. Moreover, the method features mild reaction conditions, operational simplicity, excellent functional group tolerance, and scalability.
Opposites attract? Mixed‐sex parents' and siblings' sport participation differentiates youth athletes' perceived parenting climates
Authors: Chu Tsz Lun (Alan) , Garst Brett J.
Published: April 2024

Guided by family systems and achievement goal theories, this study examined how the sex of athletes and their main sport parents, as well as sport participation patterns (same sport, different sports, and no sports) of parent–athlete and sibling sex compositions (same‐sex and mixed‐sex), differentiated athlete perceptions of parenting climates—task‐involving (emphasizing individual improvements, effort, and mastery) and ego‐involving (emphasizing winning and performance comparison). Participants were 353 U.S. high school athletes (Mage = 15.52 and SD = 1.18; 55% male) who completed a survey on perceived parenting climates, family compositions, and sport backgrounds of their parents and siblings. We conducted six moderated regression analyses, two of which used (1) athlete sex and main sport parents' sex, (2) sport participation patterns of parent–athlete sex compositions, or (3) sport participation patterns of sibling sex compositions as independent variables. Four of the analyses were statistically significant with small effect sizes, showing that (1) boys perceived greater ego‐involving climates than girls; (2) athletes whose same‐sex parents played sports (same or different sports) compared to no sports‐perceived greater task‐involving climates: (3) athletes whose mixed‐sex parents played (same or different sports) compared to no sports‐perceived greater task‐involving climates and less ego‐involving climates; and (4) athletes whose mixed‐sex siblings played different sports than they did, compared no sports, and perceived greater task‐involving climates. None of the interactions were significant. Findings provide theoretical and practical implications by incorporating motivational climates, addressing the potential relationships of parents' and mixed‐sex siblings' sport participation to adaptive parenting climates.
Pointwise data depth for univariate and multivariate functional outlier detection
Authors: Jiménez‐Varón Cristian F. , Harrou Fouzi , Sun Ying
Published: April 2024

Data depth is an efficient tool for robustly summarizing the distribution of functional data and detecting potential magnitude and shape outliers. Commonly used functional data depth notions, such as the modified band depth and extremal depth, are estimated from pointwise depth for each observed functional observation. However, these techniques require calculating one single depth value for each functional observation, which may not be sufficient to characterize the distribution of the functional data and detect potential outliers. This article presents an innovative approach to make the best use of pointwise depth. We propose using the pointwise depth distribution for magnitude outlier visualization and the correlation between pairwise depth for shape outlier detection. Furthermore, a bootstrap‐based testing procedure has been introduced for the correlation to test whether there is any shape outlier. The proposed univariate methods are then extended to bivariate functional data. The performance of the proposed methods is examined and compared to conventional outlier detection techniques by intensive simulation studies. In addition, the developed methods are applied to simulated solar energy datasets from a photovoltaic system. Results revealed that the proposed method offers superior detection performance over conventional techniques. These findings will benefit engineers and practitioners in monitoring photovoltaic systems by detecting unnoticed anomalies and outliers.
Precipitation adjustment by the OTT Parsivel2 in the central Qinghai–Tibet Plateau
Authors: Wang Chong , Zhao Lin , Ma Lu , Hu Guojie , Zhang Lele , Zou Defu , Xing Zanpin , Xiao Yao , Zhou Huayun , Qiao Yongping , Wang Yuanwei , Liu Aili , Xiao Minxuan , Zhao Jianting
Published: April 2024

Ground observation of precipitation is fundamental in preparing and evaluating various precipitation datasets, which are essential for running hydrologic and climatologic models. The undercatch of traditional precipitation gauges leads to significant uncertainty in ground observation, which is particularly severe in the central Qinghai–Tibet Plateau (QTP). To evaluate the undercatch biases, intercomparison experiments between Geonor T‐200B, the Chinese standard precipitation gauge (CSPG), and OTT Parsivel2 disdrometer were conducted at Tanggula (TGL) and Wudaoliang (WDL) sites. The adjustment schemes for 30‐min and daily precipitation were proposed and applied to 30‐min precipitation at TGL over 10 years and the monthly precipitation of the national meteorological stations on the QTP over 37 years. The results indicated that after adjustment the annual precipitation increased by 49.09% at TGL and 16.41% over the QTP. Snow took up 9.91% of the annual precipitation over the QTP, while it took up over 60% at TGL. Because of the high snow proportion, the central QTP had lower catch ratio and higher adjustment ratio than the QTP average. From 1981 to 2017, the central QTP presented a wetter trend, and the annual precipitation increased by 3.15 mm/yr, higher than the QTP average. Moreover, in the central QTP, precipitation increased more in wet than dry seasons, which were 2.45 and 0.83 mm/yr, respectively. While on the entire QTP, the dry season precipitation increased slightly more than the wet season, which were 0.67 and 0.50 mm/yr, respectively. On the QTP, adjustment amount presented an increasing trend from the northwest to the southeast, whereas annual adjustment ratio was the opposite. This study could enhance the knowledge of precipitation characteristics over the QTP, especially in the central region. More effort will be given to the calibration and uncertainty evaluation of the proposed schemes in future work.
Quaternary evolution of the Jinshan Gorge and Yellow River: Insight from numerical modelling and terrace correlation
Authors: Liu Ya , Wang Jun‐Kang , Zhang Jia‐Fu
Published: April 2024

The evolution of the Jinshan Gorge in the middle reaches of the Yellow River in China has long been a topic of debate. Previous studies have primarily focused on the connection between the Sanmen Gorge and Jinshan Gorge, attributing this connection to the Yellow River's carving through the pre‐Cenozoic bedrock areas of the Sanmen Basin. However, the patterns of knickpoint propagation along the river, influenced by tectonic upheaval and base‐level changes, have yet to be explored, despite their potential to understand fluvial system and canyon evolution. In this study, we address this issue by employing forward and inverse numerical modelling of longitudinal profiles of the Jinshan Gorge of the Yellow River and its tributaries and correlating the river terraces in this reach. We investigated 18 terrace profiles to explore their formation processes. The results demonstrated that the steepness index (Ksn) values and the incision rates of tributaries increase downstream, aligning with the relationship between knickpoint elevation and proximity to the Hancheng Fault. The knickpoint propagation appears to be related to the tectonic activities of the Hancheng Fault before 130 ka and then was influenced by climatic change, resulting in the development of five‐stage knickpoints (named Kp1, Kp2, Kp3, Kp4 and Kp5 from old to young) that correlate with the formation of terraces in the downstream area. We calculated the formation ages of Kps 1–4 to be 1.59 ± 0.06, 0.94 ± 0.11, 0.57 ± 0.31 and 0.22 ± 0.14 Ma, respectively. Kps 1, 2 and 4 correspond to the formation of the Yellow River terraces with the ages of 1.24, 1.12 and 0.24 Ma, which were reported previously. The formation of the oldest knickpoint can be correlated to the establishment of the modern course of the Yellow River in this region, which is deduced to be ~1.59 Ma.
Outcome of early detection approach in control of breast, cervical, and oral cancer: Experience from a rural cancer center in India
Authors: Budukh Atul , Dora Tapas , Sancheti Sankalp , Singh Vikram , Goel Alok , Bagal Sonali , Kaur Amandeep , Manchanda Ishan , Kaur Gurwinder , Gulia Ashish , Chaturvedi Pankaj , Badwe Rajendra
Published: April 2024

In low‐ and middle‐income countries most of the cancer patients attend the hospital at a late stage and treatment completion of these cases is challenging. The early detection program (EDP), in rural areas of Punjab state, India was initiated to identify breast, cervical, and oral cancer at an early stage by raising awareness and providing easy access to diagnosis and treatment. A total of 361 health education programs and 99 early detection clinics were organized. The symptomatic and self‐interested (non‐symptomatic individuals who opted for screening) cases visited the detection clinic. They were screened for breast, cervical, and/or oral cancer. Further diagnosis and treatment of screen‐positive cases were carried out at Homi Bhabha Cancer Hospital (HBCH), Sangrur. Community leaders and healthcare workers were involved in all the activities. The EDP, Sangrur removed barriers between cancer diagnosis and treatment with the help of project staff. From 2019 to 2023, a total of 221,317 populations were covered. Symptomatic and self‐interested individuals attended the breast (1627), cervical (1601), and oral (1111) examinations. 46 breast (in situ‐4.3%; localized‐52.2%), 9 cervical (localized‐77.8%), and 12 oral (localized‐66.7%) cancer cases were detected, and treatment completion was 82.6%, 77.8%, and 50.0%, respectively. We compared cancer staging and treatment completion of cases detected through EDP with the cases attended HBCH from Sangrur district in 2018; the difference between two groups is statistically significant. Due to the early detection approach, there is disease down‐staging and improvement in treatment completion. This approach is feasible and can be implemented to control these cancers in low‐ and middle‐income countries.