bluuebunny/crossref_metadata_2025 huggingface dataset:
Phase‐Coherent Transport in GeSn Alloys on Si
Authors: Kaul Prateek , Concepción Omar , Wielens Daan H. , Zellekens Patrick , Li Chuan , Ikonic Zoran , Ishibashi Koji , Zhao Qing‐Tai , Brinkman Alexander , Grützmacher Detlev , Buca Dan
Published: November 2024

Germanium‐Tin (GeSn) is a novel semiconductor Group IV alloy that can be tuned from indirect to direct bandgap semiconductors by adjusting the Sn content. This property makes this alloy class attractive for integrated photonic applications and high‐mobility electronic devices. In this work, the GeSn alloy properties are investigated in the view of applications fields such as spintronics and quantum computing. Using low‐temperature magneto‐transport measurements, electron interference effects and deriving typical mesoscopic benchmark parameters such as the phase‐coherence length in GeSn‐based Hall bar structures for Sn concentrations up to 14 at.% is investigated. Furthermore, Shubnikov–de Haas oscillations provide direct access to the effective mass of the Γ‐valley electrons as well as the charge carrier mobility. This work provides a new insight into advanced group IV alloys desired for the study of spin dynamics and its quantum computing applications.
Assessing management factors limiting yield and starch content of cassava in the western Brazilian Cerrado
Authors: Zebalho Cleiton Simão , Pilecco Isabela Bulegon , Streck Nereu Augusto , Cardoso Paula de Souza , Freitas Charles Patrick de Oliveira de , Vieira Eduardo Alano , Soares Mauricio Fornalski , Tagliapietra Bruna Lago , Ferigolo Alexandre Alves , Swarowsky Alexandre , Follmann Diego Nicolau , Souza João Vitor Santos de , Zanon Alencar Junior
Published: October 2024

Cassava (Manihot esculenta Crantz) was declared the “crop of the 21st century” by the Food and Agriculture Organization of the United Nations due to its high starch content and low input requirements. The management factors that govern yields and starch content in cassava in Brazil are still unclear. The aim of this study was to identify the main factors that limit the yield and starch content of cassava fields in Brazilian Cerrado. The data were collected as part of a survey covering 300 cassava fields in two growing seasons (2020–2021 and 2021–2022). Throughout the development cycle, management practices, yield, and percentage starch content in the roots were described. The database was divided into high and low yield tertiles. Mean comparison tests, regression tree analyses, and boundary functions were applied. The importance of genetics, environment, and associated crop constraints on cassava production (yields and starch content) was assessed. The yield gap in cassava was 44.6 Mg ha−1. The most important factors leading to yield and starch losses were variety, planting date, and potassium fertilization. By adapting optimal practices, it is possible to produce an additional 1.5 million tons of cassava on the current cultivation area in the western Brazilian Cerrado, which corresponds to 8.3% of total production in Brazil and could increase the production of cassava starch by more than 400,000 Mg.
Widespread male sterility and trioecy in androdioecious Mercurialis annua: Its distribution, genetic basis, and estimates of morph‐specific fitness components
Authors: Nguyen Mai Thu , Martignier Thomas , Pannell John R.
Published: November 2024

Premise

Angiosperms range in sexual system from hermaphroditism through gynodioecy and androdioecy to dioecy. Trioecy, where females and males coexist with hermaphrodites, is rare. Recently, trioecy was documented in hexaploid populations of the wind‐pollinated herb Mercurialis annua in Spain.

Methods

We surveyed the frequency of males, hermaphrodites, and females in M. annua across its distribution in the Iberian Peninsula, tracked sex‐ratio variation in several populations over consecutive generations, and assessed evidence for pollen limitation. In a common garden, we estimated male, female, and hermaphroditic fitness. We used controlled crosses to infer the genetic basis of male sterility. Finally, we compared predictions of a deterministic model with the distribution of observed sex ratios in the field based on our fitness estimates and the inferred genetics of sex determination.

Results

Trioecy is widespread in Spanish and Portuguese populations of M. annua. Males are determined by a dominant (Y‐linked) allele, and female expression results from the interaction between cytoplasmic male sterility and multiple nuclear male sterility restorers partially linked to the male determiner. Male pollen production is approximately 12 times that of hermaphrodites, while female seed production is less than 1.12 times the observed hermaphroditic levels. The distribution of sex ratios in natural populations conforms with predictions of our deterministic simulations.

Conclusions

Our study documents and accounts for a clear case of trioecy in which sex is determined by both maternally and biparentally inherited genes.
Membrane‐Free Water Electrolysis for Hydrogen Generation with Low Cost
Authors: Gao Xintong , Wang Pengtang , Sun Xiaogang , Jaroniec Mietek , Zheng Yao , Qiao Shi‐Zhang
Published: October 2024

Conventional water electrolysis relies on expensive membrane‐electrode assemblies and sluggish oxygen evolution reaction (OER) at the anode, which makes the cost of green hydrogen (H2) generation much higher than that of grey H2. Here, we develop an innovative and efficient membrane‐free water electrolysis system to overcome these two obstacles simultaneously. This system utilizes the thermodynamically more favorable urea oxidation reaction (UOR) to generate clean N2 over a new class of Cu‐based catalyst (CuXO) for replacing OER, fundamentally eliminating the explosion risk of H2 and O2 mixing while removing the need for membranes. Notably, this membrane‐free electrolysis system exhibits the highest H2 Faradaic efficiency among reported membrane‐free electrolysis work. In situ spectroscopic studies reveal that the new N2Hy intermediate‐mediated UOR mechanism on the CuXO catalyst ensures its unique N2 selectivity and OER inertness. More importantly, an industrial‐type membrane‐free water electrolyser (MFE) based on this system successfully reduces electricity consumption to only 3.78 kWh Nm−3, significantly lower than the 5.17 kWh Nm−3 of commercial alkaline water electrolyzers (AWE). Comprehensive techno‐economic analysis (TEA) suggests that the membrane‐free design and reduced electricity input of the MFE plants reduce the green H2 production cost to US$1.81 kg−1, which is lower than those of grey H2 while meeting the technical target (US$2.00–2.50 kg−1) set by European Commission and United States Department of Energy.
Promoting Charge‐Carriers Dynamics by Relaxed Lattice Strain in A‐site‐Doped Halide Perovskite for Photocatalytic H2 Evolution
Authors: Guo Qing , Zhang Jin‐Dan , Liu Jia‐Mei , Chen Ya‐Jing , Qin Bin , Xia Jing , Guo Li‐Na , Duan Xin‐Hua , Wu Li‐Zhu
Published: October 2024

Because of the unique and superior optoelectronic properties, metal halide perovskites (MHPs) have attracted great interest in photocatalysis. Element doping strategy is adopted to modify perovskite materials to improve their photocatalytic performance. However, the contribution of bare doping‐site onto photocatalytic efficiency, and the correlation between doping locations and activity have not yet to be demonstrated. The unique properties of non‐active alkali metals promoted us to systematically explore the potential of A‐site‐doped MHPs for photocatalysis. Herein, we dope potassium (K+) into CsPbBr3 via an anti‐solvent precipitation method and first reveal that the occupied locations of K+ in CsPbBr3 is lattice incorporation rather than surface segregation, which would change from A‐site substitution to interstitial site in lattice with the increase of K+ concentrations. Taking hydrogen (H2) evolution as a model reaction, photocatalytic activity of CsPbBr3 after K+ doping could be significantly improved ~11‐fold with A‐site substitution, which is superior to that of interstitial site doping. Moreover, other alkali metals including lithium (Li), sodium (Na), and rubidium (Rb) doping give the same results. The structure of photocatalysts during reaction confirmed the contribution of A‐site doping onto enhanced photocatalytic activity. Mechanistic insights show it is a result of the relaxed lattice strain induced promoted charge‐carriers dynamics and upward shifting of band after K+ A‐site doping.
The Hard Ferromagnetism in FePS3 Induced by Non‐Magnetic Molecular Intercalation
Authors: Ou Yunbo , Li Xiaoyin , Kopaczek Jan , Davis Austin , Jackson Gigi , Sayyad Mohammed , Liu Feng , Tongay Seth Ariel
Published: November 2024

Manipulating the magnetic ground states of 2D magnets is a focal point of recent research efforts. Various methods have demonstrated efficacy in modulating the magnetic properties inherent to van der Waals (vdW) magnetic systems. Herein, the emergence of robust anisotropic ferromagnetism within antiferromagnetic FePS3 is unveiled via intercalation with non‐magnetic pyridinium ions. A one‐step ion exchange reaction facilitates the formation of energetically favorable B‐phase and metastable P‐phase. Notably, both B‐ and P‐phases manifest hard ferromagnetic behavior, featuring substantial unsaturated coercive fields (>7 T) and high Curie temperatures (72–87 K). First‐principles calculations elucidate the pivotal role of electron transfer from pyridinium ions to FePS3 in engineering magnetic exchange interactions. Calculated effective spin Hamiltonian corroborates the observed hard ferromagnetism in intercalated FePS3. This study offers crucial insights into hard magnetism in intercalated vdW materials, thereby presenting promising avenues for 2D vdW magnet‐based magnetic devices.
A Single Cell Transcriptomic Fingerprint of Stressed Premature, Imbalanced Differentiation of Embryonic Stem Cells
Authors: L Ruden Ximena , Singh Aditi , Marben Teya , Tang Wen , O Awonuga Awoniyi , Ruden Douglas M. , E Puscheck Elizabeth , Feng Hao , Korzeniewski Steven J. , A Rappolee Daniel
Published: November 2024

Background

Miscarriages cause a greater loss‐of‐life than cardiovascular diseases, but knowledge about environmentally induced miscarriages is limited. Cultured naïve pluripotent embryonic stem cells (ESC) differentiate into extra‐embryonic endoderm/extraembryonic endoderm (XEN) or formative pluripotent ESC, during the period emulating maximal miscarriage of peri‐implantation development. In previous reports using small marker sets, hyperosmotic sorbitol, or retinoic acid (RA) decreased naïve pluripotency and increased XEN by FACS quantitation.

Methods

Bulk and single cell (sc)RNAseq analyses of two cultured ESC lines was done, corroborated by qPCR. Transcriptomic responses were analyzed of cultured ESC stressed by Sorbitol, with Leukemia inhibitory factor (LIF + ; stemness growth factor), RA without LIF to control for XEN induction, and compared with normal differentiation (LIF − , ND).

Results

Sorbitol and RA increase subpopulations of 2‐cell embryo‐like (2CEL) and XEN sub‐lineages; primitive, parietal, and visceral endoderm (VE) cells and suppress formative pluripotency, imbalancing alternate lineage choices of initial naïve pluripotent cultured ESC compared with ND. Although bulk RNAseq and gene ontology (GO) group analyses suggest that stress induces anterior VE‐head organizer and placental markers, scRNAseq reveals relatively few cells. But VE and placental markers/cells were in adjacent stressed cell clusters in the UMAP, like recent, normal UMAP of conceptuses. UMAPs show that dose‐dependent stress overrides stemness to force premature lineage imbalance.

Conclusions

Hyperosmotic stress, and other toxicological stresses, like drugs with active ingredient RA, may cause premature, lineage imbalance, resulting in miscarriages or birth defects.
Machine learning models reveal ARHGAP11A's impact on lymph node metastasis and stemness in NSCLC
Authors: Wang Xiaoli , Zhou Yan , Lu Xiaomin , Shao Lili
Published: November 2024

Most patients with non‐small cell lung cancer (NSCLC) are diagnosed at an advanced stage of the disease, which complicates treatment due to a heightened risk of metastasis. Consequently, the timely identification of biomarkers associated with lymph node metastasis is essential for improving the clinical management of NSCLC patients. In this research, the WGCNA algorithm was utilized to pinpoint genes linked to lymph node metastasis in NSCLC. A cluster analysis was carried out to investigate how these genes correlate with the prognosis and the outcomes of immunotherapy for NSCLC patients. Following this, diagnostic and prognostic models were created and validated through various machine learning methodologies. The random forest technique highlighted the importance of ARHGAP11A, leading to an in‐depth examination of its role in NSCLC. By analyzing 78 tissue chip samples from NSCLC patients, the study confirmed the association between ARHGAP11A expression, patient prognosis, and lymph node metastasis. Finally, the influence of ARHGAP11A on NSCLC cells was assessed through cell function experiments. This research utilized the WGCNA technique to identify 25 genes that are related to lymph node metastasis, clarifying their connections with tumor invasion, growth, and the activation of stemness pathways. Cluster analysis revealed significant associations between these genes and lymph node metastasis in NSCLC, especially concerning immunotherapy and targeted treatments. A diagnostic system that combines various machine learning approaches demonstrated strong efficacy in forecasting both the diagnosis and prognosis of NSCLC. Importantly, ARHGAP11A was identified as a key prognostic gene associated with lymph node metastasis in NSCLC. Molecular docking analyses suggested that ARHGAP11A has a strong affinity for targeted therapies within NSCLC. Additionally, immunohistochemical assessments confirmed that higher levels of ARHGAP11A expression correlate with unfavorable outcomes for NSCLC patients. Experiments on cells showed that reducing ARHGAP11A expression can hinder the proliferation, metastasis, and stemness traits of NSCLC cells. This investigation reveals the novel insight that ARHGAP11A may function as a potential biomarker connected to lymph node metastasis in NSCLC. Moreover, reducing the expression of ARHGAP11A has demonstrated the ability to diminish tumor stemness characteristics, presenting a promising opportunity for improving treatment strategies for this condition.
Progress on the Mechanisms and Neuroprotective Benefits of Dexmedetomidine in Brain Diseases
Authors: Tao Zhenxing , Li Pengpeng , Zhao Xudong
Published: November 2024

Introduction

Dexmedetomidine, a highly specific α2 agonist, has been extensively utilized in clinical sedation and surgical anesthesia since its introduction in 2000 due to its excellent sympatholytic, sedative, and analgesic effects. This review aimed to identify new approaches for the treatment of patients with brain disorders by thoroughly describing the mechanism of action of dexmedetomidine and examining its neuroprotective effects from the standpoints of basic and clinical research.

Methods

The PubMed and Web of Science databases were searched using the keywords dexmedetomidine and related brain diseases, although relevant articles from the last decade were included for detailed summarization and analysis.

Results

Dexmedetomidine has shown strong neuroprotective effects, such as protection of the blood‐brain barrier, decreased neuronal death, maintained hemodynamic stability, and reduced postoperative agitation and cognitive dysfunction. Furthermore, dexmedetomidine has been shown to exert various neuroprotective effects, including anti‐inflammatory and antioxidative stress effects, modulation of autophagy, and reduction of apoptosis in cerebral diseases.

Conclusions

Dexmedetomidine acts as a neuroprotective agent against brain diseases during all phases of treatment. However, clinical trials with larger sample sizes are required to optimize dosage and dosing strategies.
Comparison of Time to Next Treatment or Death Between Front‐Line Daratumumab, Lenalidomide, and Dexamethasone (DRd) Versus Bortezomib, Lenalidomide, and Dexamethasone (VRd) Among Transplant‐Ineligible Patients With Multiple Myeloma
Authors: Hansen Doris K. , Gautam Santosh , Lafeuille Marie‐Hélène , Rossi Carmine , Moore Bronwyn , Tardif‐Samson Anabelle , Thompson‐Leduc Philippe , Fu Alex Z. , Cortoos Annelore , Kaila Shuchita , Fonseca Rafael
Published: November 2024

Introduction

Daratumumab, lenalidomide, and dexamethasone (DRd) and bortezomib, lenalidomide, and dexamethasone (VRd) are the only preferred treatment regimens for patients with transplant‐ineligible (TIE) newly diagnosed multiple myeloma (NDMM). As there are no randomized head‐to‐head studies of DRd versus VRd, this analysis aimed to compare real‐world time‐to‐next‐treatment (TTNT) or death in this population.

Methods

Patients with NDMM who received front‐line (FL) DRd or VRd were identified from the Acentrus database (January 1, 2018 to May 31, 2023). Those with a record of a stem cell transplant or aged < 65 years were excluded to limit analysis to the TIE population. Inverse probability of treatment weighting was used to balance baseline patient characteristics. A doubly robust Cox proportional hazards model was used to compare TTNT or death between cohorts.

Results

A total of 149 and 494 patients who initiated DRd and VRd, respectively, were identified. After weighting (weighted NDRd = 302, weighted NVRd = 341), cohorts had similar baseline characteristics. Of these, 98 (32.4%) DRd and 175 (51.2%) VRd patients either received a subsequent line of therapy or died, with a median TTNT or death of 37.8 months in the DRd cohort and 18.7 months in the VRd cohort (hazard ratio: 0.58, 95% confidence interval: 0.35, 0.81; p < 0.001).

Conclusion

Treatment of TIE NDMM patients with DRd led to a significantly longer TTNT or death compared to VRd, evidenced by a 42% risk reduction, supporting the effectiveness of DRd over VRd as FL treatment in this patient population.
Important Roles of PI3K/AKT Signaling Pathway and Relevant Inhibitors in Prostate Cancer Progression
Authors: Wang Rui , Qu Zhen , Lv Ying , Yao Lu , Qian Yang , Zhang Xiangyu , Xiang Longquan
Published: November 2024

Prostate cancer (PCa) is an extremely common malignant tumor of the male genitourinary system, originating from the prostate gland epithelium. Male patients are prone to relapse after treatment, which seriously threatens their health. Phosphoinositide 3‐kinase (PI3K)/protein kinase B (PKB, also known as Akt) plays an important role in the growth, invasion, and metastasis of PCa. This review aimed to present an overview of the mechanism of action of the PI3K/AKT signaling pathway in PCa and discuss the application prospects of inhibitors of this pathway in treating PCa, providing a theoretical basis and reference for its clinical treatment targets.
Linear and Polyvalent Peptides with Potent Antimicrobial Activity Against Sensitive and Multidrug‐Resistant E. c oli Clinical Isolates
Authors: Cuero‐Amu Kelin , Daniela Bonilla‐Velásquez Laura , Vargas‐Casanova Yerly , Lucía Leal‐Castro Aura , Marcela Parra‐Giraldo Claudia , Giselle López‐Sánchez Amalia , Fierro‐Medina Ricardo , García‐Castañeda Javier , Rivera‐Monroy Zuly
Published: November 2024

Peptides containing the sequences 20RRWQWR25 and 20RRWQWRMKKLG30 derived from Bovine lactoferricin (LfcinB) were synthesized and their antibacterial effect against reference strains and sensitive and resistant clinical isolates of E. coli was evaluated. Tetra‐branched multiple antigen peptide (MAP) ((RRWQWR)2‐K‐Ahx‐C)2 exhibited significant antibacterial activity against sensitive, resistant, and multidrug‐resistant clinical isolates of E. coli. Peptide 3: RRWQWR‐Nal‐KKLG; MIC=16 μM, 26[F]: (RRWQWRFKKLG)2‐K‐Ahx; MIC=15 μM, 17: (RRWQWRFK)2‐K‐Ahx; MIC=9 μM, and LfcinB (20–25)2: (RRWQWR)2‐K‐Ahx; MIC=11 μM exhibited the highest antibacterial activity against E. coli strains, with bactericidal effect and haemolytic effect at MIC less than 5 % and a therapeutic index >1. A synergistic effect of peptides 26[F] and 17 with ciprofloxacin (CIP) or ceftriaxone (CEF) was observed. Prolonged treatment of E. coli ATCC 25922 with sublethal concentrations of CIP induced resistance in this strain, whereas some peptides did not induce resistance. These peptides can be considered to be promising candidates for treating infections caused by resistant strains of E. coli.
Investigation into the Quantitative Structure‐Biotoxicity Relationship of Antibiotics and their Estrogenic Receptor Disruption Effects
Authors: Zhu Wanhong , Chen Shuangkou , Wang Yu , Xu Xi , Huang Xia , Yang Xin , Ren Fengming
Published: November 2024

In light of antibiotics being classified as environmental hormone‐like compounds, their interference with the endocrine system has significantly impacted human health and ecological environments. This study employed Density Functional Theory (DFT) within Gaussian09, conducting structural optimizations and property calculations on 23 typical antibiotic molecules at the B3LYP/3‐21G and B3LYP/6‐31G(d) levels to obtain structural parameters and acquired physicochemical property parameters through the RDKit database in ChemDes platform for quantitative processing of the compounds. Multiple linear regression analysis identified the primary factors affecting antibiotics’ biological toxicity (pLD50), and a QSAR model was established. The model's predictive capability was analyzed using leave‐one‐out cross‐validation, and the binding modes and mechanisms of action between estrogen receptors (ER) and antibiotics were investigated via molecular docking and molecular dynamics simulations. The results indicate that six property parameters significantly influence the biological toxicity of antibiotics, with the established QSAR model C exhibiting regression coefficients R2 and Q2 of 0.92474 and 0.74913, respectively, demonstrating good stability and predictive power. Molecular surface electrostatic potential, frontier molecular orbitals, molecular docking, and molecular dynamics simulations revealed that stable hydrogen bonds and hydrophobic interactions primarily mediate the potential estrogenic disrupting effects between antibiotics and estrogen receptors. Predictions from an anticancer compound library identified ten compounds with strong estrogenic disrupting effects, and molecular docking validated the practical utility of model C. This provides a valuable exploration for discovering and screening PPCPs with potential estrogenic disrupting effects.
Design, Synthesis, and Anti‐Inflammatory Activity Evaluation of Novel Indanone Derivatives for the Treatment of Vascular Dementia
Authors: Tang Xue‐Song , He Lin‐Yu , Li Sheng‐Nan , Zhang Wen‐Cheng , Wu Ze‐Yu , Hui Ai‐Ling
Published: November 2024

Vascular dementia (VaD) is a neurodegenerative disease resulting from cerebral vascular obstruction, leading to cognitive impairment, and currently lacks effective treatment options. Due to its complex pathogenesis, multi‐target drug design (MTDLs) strategies are considered among the most promising therapeutic approaches. In this study, we designed and synthesized a series of novel indanone derivatives targeting targets related to vascular health and dementia. The results indicated that compound C5 exhibited excellent acetylcholinesterase inhibitory activity (IC50 =1.16 0.41 μM) and anti‐platelet aggregation activity (IC50 =4.92±0.10 μM) within ranges of 0.1–1000 μM and 0.03–300 μM, respectively, possibly mediated by molecular docking interactions. Furthermore, compound C5 demonstrated protective effects on cells at concentrations ≤50 μM, significantly reducing the release of nitric oxide (NO), tumor necrosis factor‐alpha (TNF‐α), and interleukin‐1 beta (IL‐1β) in a concentration‐dependent manner, showcasing its potent neuroinflammatory inhibitory effects. Anti‐inflammatory therapies are regarded as effective strategies for treating VaD. Therefore, compound C5 holds promise as a novel candidate drug for further investigation into the treatment of vascular dementia.
Classification of primary mitral regurgitation using extramitral cardiac involvement in patients undergoing transcatheter edge‐to‐edge repair
Authors: Kaewkes Danon , Shechter Alon , Patel Vivek , Koren Ofir , Koseki Keita , Chakravarty Tarun , Nakamura Mamoo , Makar Moody , Makkar Raj
Published: November 2024

Background

An enhanced classification of primary mitral regurgitation (PMR) based on extramitral cardiac involvement may refine patient selection and optimize the timing of transcatheter edge‐to‐edge repair (TEER).

Aims

This study aimed to assess the prognostic significance of a recently established classification system that characterizes the extent of extramitral cardiac damage in patients undergoing TEER for PMR.

Methods

Consecutive PMR patients who received MitraClip implantation were categorized according to the presence of extramitral cardiac damage, determined through preprocedural echocardiography. The classifications included no damage or only left ventricular dilatation (group 0), left atrial involvement (group 1), right ventricular volume/pressure overload (group 2), right ventricular failure (group 3), or left ventricular failure (group 4). Cox‐proportional hazard models were used to ascertain the impact of PMR groups on the primary composite outcome of all‐cause mortality or rehospitalization for heart failure (HHF) over 2 years.

Results

In a cohort of 322 eligible PMR patients undergoing TEER (median age: 83 years; 41% female) between 2013 and 2020, the following distribution emerged: group 0 (10 patients, 3%), group 1 (96 patients, 30%), group 2 (117 patients, 36%), group 3 (56 patients, 18%), and group 4 (43 patients, 13%). Kaplan‐Meier analysis demonstrated a significant decline in freedom from the primary outcome as group severity increased (log‐rank p = 0.030). On multivariate analysis, the degree of extramitral cardiac involvement was significantly associated with the primary outcome (HR: 1.30; 95% CI: 1.02–1.67; p = 0.043), primarily driven by HHF.

Conclusions

This innovative classification system for PMR, based on extramitral cardiac involvement, carries significant prognostic implications for clinical outcomes following TEER. Integrating this classification system into clinical decision‐making could enhance risk stratification and optimize the timing of TEER in these patients.
Sump syndrome: Diagnosis dilemmas and therapeutic approaches—A case series
Authors: Abbarh Shahem , Sawaf Bisher , Almasri Hussam , Balaraju Girisha , Albuni Mhd Kutaiba , Abbarah Shaher , Ahmed Ashraf I. , Ismail Abdellatif , Al Kaabi Saad Rashid Mohammad
Published: November 2024

Key Clinical Message

It is important to consider the diagnosis of Sump syndrome in patients with a history of open cholecystectomy, particularly in those who migrate from developing countries where alternative biliary interventions may be limited. The presentation may range from acute severe, mimicking acute ascending cholangitis, to chronic recurrent abdominal pain without evidence of inflammation. Management is a case‐by‐case decision, with principal management aims to decompress the biliary tract and address any underlying sepsis.

Sump syndrome is a rare and often long‐term complication of choledochoduodenostomy (CDD). The presentation and severity are variable, and management should be tailored to each patient based on several factors. Herein, we report three cases of sump syndrome, each demonstrating unique diagnostic dilemmas and therapeutic modalities. Case I describes a woman presenting with acute cholangitis, managed with percutaneous transhepatic cholangiography (PTC) and endoscopic retrograde cholangiopancreatography (ERCP). Case II illustrates a similar presentation complicated by myocardial infarction, necessitating urgent biliary decompression via PTC and subsequent unsuccessful endoscopic stenting. Case III highlights the diagnostic difficulty in a stable patient with inconclusive diagnostic imaging. This case series emphasizes the importance of considering sump syndrome diagnosis in patients with a history of CDD or open cholecystectomy, especially in elderly patients and those who come from regions where alternative biliary interventions may be limited.
Hip pain and exophthalmos in a child: Which diagnosis?
Authors: Arfa Wajdi , Ghammem Mohamed , Kamoun Khaled Anis , Jenzri Mourad , Jlalia Zied
Published: November 2024

Key Clinical Message

This case is a reminder that bone pain in children can reflect a general pathology or a distant lesion. Thus, it is important to look for other associated signs, such as exophthalmos in our case which led us to the diagnosis of neuroblastoma metastasized to the bone.
Necrotizing fasciitis resembled acute coronary syndrome: A case report
Authors: Sepehrinia Matin , Yousefi Faeze , Valibeygi Adib , Alkamel Abdulhakim
Published: November 2024

Key Clinical Message

Chest pain is a frequent complaint in emergency departments, with various differential diagnoses from benign to life‐threatening. Hereby, we described a 60‐year‐old man presented with chest pain and hypotension who initially misdiagnosed as acute coronary syndrome, but was ultimately diagnosed with necrotizing fasciitis. This case highlights the importance of considering rare causes of chest pain.
A rare case of systemic lupus erythematosus presenting with concurrent myocarditis, central retinal vein occlusion, and deep vein thrombosis
Authors: Fesharaki Mehrdad Jafari , Zakeri Zahra , Hosseinjani Emadoddin , Dehkordi Nastaran Raissi
Published: November 2024

Key Clinical Message

Although systemic lupus erythematosus may present with broad and variable symptoms, the rare and atypical combined presentation of central retinal vein occlusion, myocarditis, and deep vein thrombosis poses a diagnostic challenge and highlights the need for a comprehensive diagnostic approach. Early diagnosis and prompt treatment help mitigate disease morbidity and mortality, and emphasize the importance of heightened clinical suspicion in complex presentations.
First case of progressive solitary sclerosis with relapsing attacks: A 49‐year‐old woman
Authors: Asadollahzadeh Elnaz , Shahmaei Vahid , Ebadi Zahra , Johari Mohammad‐Sadegh , Rezaeimanesh Nasim , Naser Moghadasi Abdorreza
Published: November 2024

Key Clinical Message

This case highlights a rare form of solitary sclerosis with a relapsing pattern, contrasting with the typical single attack and nonrelapsing nature of the disease. Despite the lack of new lesions on MRI, This case demonstrates that, despite the rarity of this variant, a relapsing form of solitary sclerosis can occur and should be considered a differential diagnosis.

Progressive solitary sclerosis is characterized by isolated demyelinating damage to the central nervous system in the spinal cord and brainstem, leading to progressive motor impairment. We describe the case of a 49‐year‐old woman who suffered several recurrent attacks of right hemiparesis over time. The patient initially responded well to methylprednisolone pulse therapy without maintenance therapy. However, subsequent episodes resulted in mild residual symptoms and the progression of her condition. Clinical examination revealed normal cranial nerve function, decreased sensation in the right limbs, and abnormal signal findings on MRI of the cervical spine. Laboratory tests, vasculitis screening, cerebrospinal fluid (CSF) analysis, and brain/spinal cord angiography were all within normal limits. Based on these findings and the patient's clinical presentation, a diagnosis of progressive solitary sclerosis with relapsing attacks was made. Rituximab treatment was initiated with administration of a first dose of 1000 mg, followed by a second dose 6 months later.
Approaching Dynamic Behaviors of Life through Systems Chemistry
Authors: Gu Ruirui , Lambertsen Larsen Kim , Wang Ali , Tan Junjun
Published: November 2024

The intricate interplay of metabolic reactions and molecular assembly in living systems enables spatiotemporally organization and gives rise to diverse dynamic behaviors that characterize life. Over the last decades, research efforts have increasingly focused on replicating the remarkable properties and characteristics of living systems, driving the rapid growth of systems chemistry. This young discipline which generally studies interacting molecular networks and emergent system‐level properties, behaviors, and functions, offers new concepts and tools to tackle the complexity of life. In this review paper, we have explored seminal research and recent advancements in recreating dynamic behaviors of life with systems chemistry. We believe that the recreation of the dynamic behaviors of life through systems chemistry would set the initial steps to obtain synthetic life de novo.
One‐Electron NO to N2O Pathways via Heme Models and Lewis Acid: Metal Effects and Differences from the Enzymatic Reaction
Authors: Chu Jia‐Min , Khade Rahul L. , Nguyen Vy , Richter‐Addo George B. , Zhang Yong
Published: October 2024

Some pathogens use heme‐containing nitric oxide reductases (NORs) to reduce NO to N2O as their defense mechanism to detoxify NO and reduce nitrosative stress. This reduction is also significant in the global N cycle. Our previous experimental work showed that Fe and Co porphyrin NO complexes can couple with external NO to form N2O when activated by the Lewis acid BF3. A key difference from conventional two‐electron enzymatic reaction is that one electron is sufficient. However, a complete understanding of the entire reaction pathways and the more favorable reactivity for Fe remains unknown. Here, we present a quantum chemical study to provide such information. Our results confirmed Fe's higher experimental reactivity, showing advantages in all steps of the reaction pathway: easier metal oxidation for NO reduction and N−O cleavage as well as a larger size to expedite the N/O coordination mode transition. The Co system, with a similar product energy as the enzyme, shows potential for further development in catalytic NO coupling. This work also offers the first evidence that this new one‐electron NO reduction is both kinetically competitive and thermodynamically more favorable than the native pathway, supporting future initiatives in optimizing NO reduction agents in biology, environment, and industry.
Cross‐Electrophile Couplings (XECs) between Similar Electrophile Reagents
Authors: Lei Jie , Yu Shan , Xu Zhi‐Gang
Published: November 2024

Comprehensive Summary

Cross‐electrophile couplings (XEC), a crucial subset of cross‐coupling reactions, center on the formation of robust C—C bonds through the union of two electrophiles. Usually, such reactions have primarily been catalyzed by transition metals. However, with the steady advancements in photochemical and electrochemical technologies, XEC reactions have significantly progressed and broadened their scope, allowing for the utilization of a wider array of tolerable functional groups, thus revealing vast application prospects. This review aims to systematically summarize the current prevalent types of electrophiles and delve into their specific application examples within XEC reactions involving electrophiles with identical functional groups. Specifically, XECs between the same type of halides have received considerable attention, whereas carboxylic acids and alcohols are still in the early stages of investigation. Furthermore, certain other common electrophiles remain unexplored in this context. Moreover, this review underscores the remarkable contributions of photochemistry and electrochemistry in the field of XEC reactions, aiming to provide valuable insights and inspiration for researchers. Also, this review hopes to spark further interest in XEC reactions, thereby fueling the continuous development and advancement of this exciting area of research.

Key Scientists

Since the 1960s, advancements in the XEC reaction have been substantial, driven primarily by the application of transition metal catalysts. In this area, many distinguished scientists have contributed their wisdom and efforts. Particularly noteworthy is that, during the systematic study of XEC reactions with the identical functional groups, in 2016, MacMillan achieved a photocatalytic XEC reaction between aryl bromides and alkyl bromides; in 2020, Weix successfully realized a nickel‐catalyzed XEC reaction between aryl chlorides and alkyl chlorides. Concurrently, contributions from researchers such as Mei, Wolf, Sevov, Lin, Shen, Browne, Zhang, and Qiu have expanded the scope of XEC reactions to various halides. By 2022, MacMillan and Baran achieved a significant milestone in the XEC between carboxylic acids, further broadening the scope of research in this area. Also, advancements in the XEC of alcohols have been noted, with researchers including Weix, Lian, Tu, and Stahl conducting pioneering work and successfully executing the XEC of protective groups. It is foreseen that the ongoing research endeavors will primarily concentrate on the expansion of diverse electrophiles.
Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters†
Authors: Zhu Yu‐Shen , Li Jia‐Xin , Zhao Hao‐Tian , Su Bo
Published: November 2024

Comprehensive Summary

Vicinal stereogenic centers are ubiquitous structural scaffolds in both natural products and synthetic compounds, yet their enantioselective construction remains a significant challenge in organic synthesis. Organoboron compounds are of paramount importance in synthetic chemistry due to their ability to undergo facile transformations, yielding diverse essential chemical bonds such as carbon‐carbon, carbon‐oxygen, carbon‐nitrogen, and carbon‐halogen bonds. Transition‐metal‐catalyzed asymmetric borylative functionalizations of internal alkenes offer a promising strategy for the enantioselective installation of two adjacent chiral centers across carbon‐carbon bonds. By leveraging the versatile transformations of the newly introduced boryl unit, this approach holds great potential for expanding the structural diversity of vicinal stereogenic scaffolds. In this concise review, we aim to highlight recent advancements in transition‐metal‐catalyzed asymmetric borylative functionalizations of internal alkenes, underscore their utility as a versatile approach for constructing vicinal stereogenic centers, and discuss unsolved challenges and future directions in this field.

Key Scientists
Role of H2O2 as Oxidant and H2O as Co‐Catalyst Over Anatase‐TiO2(101) for Conversion of Methane to Methanol
Authors: Charakhwal Kanishka , Agarwal Vishal
Published: November 2024

Computations based on density functional theory are carried out to examine the mechanism of photocatalytic oxidation of methane to methanol with H2O2 as oxidant and water as co‐catalyst over anatase TiO2(101) surface. The reaction proceeds with hydrogen abstraction from methane followed by the formation of surface methoxy species, which is reduced to methanol. We compare the reaction energetics for C−H dissociation in the presence and absence of surface defect, but find no discernible impact of O‐vacancy on methane oxidation. In comparison, hydroxyl produced as a result of H2O2 or H2O photo‐decomposition dramatically reduces the barrier for CH3‐H bond cleavage. The reaction proceeds further by the reduction of surface methoxy group and is the rate‐limiting step for methanol formation. Additionally, we find that methyl can also react with water to form methanol with a considerably lower barrier, suggesting an active involvement of water for methanol formation. We also study the role of water as a co‐catalyst and observe significant reduction in barriers, facilitated by alternate pathway for proton transfer. The reaction pathways presented provide valuable insights into the mechanism of methane oxidation in the presence of H2O2 as oxidant and demonstrate the rate‐enhancing role of water for these steps.
Deciphering the Ce3+ to Ce4+ Evolution: Insight from X‐ray Raman Scattering Spectroscopy at Ce N4,5 Edges
Authors: Das Soumya K. , Longo Alessandro , Bianchi Eugenio , Bordenca Claudio V. , Sahle Christoph J. , Pia Casaletto Maria , Mirone Alessandro , Giannici Francesco
Published: October 2024

Cerium oxide, or ceria, (CeO2) is one of the most studied materials for its wide range of applications in heterogeneous catalysis and energy conversion technologies. The key feature of ceria is the remarkable oxygen storage capacity linked to the switch between Ce4+ and Ce3+ states, in turn creating oxygen vacancies. Changes in the electronic structure occur with oxygen removal from the lattice. Accordingly, the two valence electrons can be accommodated by the reduction of support cations where the electrons can be localized in empty f states of Ce4+ ions nearby due to small polaron hopping resulting in the formation of Ce3+. Quantifying the different oxidation states in situ is crucial to understand and model the reaction mechanism.

Beside the different techniques that have been used to quantify Ce3+ and Ce4+ states, we discuss the use of X‐ray Raman Scattering (XRS) spectroscopy as an alternative method. In particular, we show that XRS can observe the oxidation state changes of cerium directly in the bulk of the materials under realistic environmental conditions. The Hilbert++ code is used to simulate the XRS spectra and quantify accurately the Ce3+ and Ce4+ content. These results are compared to those obtained from in situ X‐ray Diffraction (XRD) collected in parallel and the differences arising from the two different probes are discussed.
Xylose Acetals ‐ a New Class of Sustainable Solvents and Their Application in Enzymatic Polycondensation
Authors: Komarova Anastasia O. , Warne Cicely M. , Pétremand Hugo , König‐Mattern Laura , Stöckelmaier Johannes , Oostenbrink Chris , Guebitz Georg M. , Luterbacher Jeremy , Pellis Alessandro
Published: October 2024

The use of organic solvents in academic research and industry applications is facing increasing regulatory pressure due to environmental and health concerns. Consequently, there is a growing demand for sustainable solvents, particularly in the enzymatic synthesis and processing of polyesters. Biocatalysts offer a sustainable method for producing these materials; however, achieving high molecular weights often necessitates use of solvents. In this work, we introduce a new class of alternative aprotic solvents with medium polarity produced directly from agricultural waste biomass in up to 83 mol % yield (on xylan basis). The new solvents have a largely unmodified xylose core and acetal functionality, yet they show no peroxide formation and provide reduced flammability risk. We also demonstrate their successful application in enzymatic polycondensation reactions with Candida antarctica lipase B (CaLB). In particular, the solvent dibutylxylose (DBX) outperformed the hazardous solvent diphenyl ether and facilitated polycondensation of the lignin‐derived diester pyridine‐2,4‐dicarboxylate, yielding polyesters with a Mn of >15 kDa. Computational modelling studies provided further insight into the molecular structure and dynamics of CaLB in the presence of new solvents. Lastly, up to 98 wt % of the new xylose acetals were successfully recovered and recycled, further contributing to the sustainability of the overall process.
Development of Enriched ROA With Dilated Hybrid Network for Automatic Modulation Classification Framework in CRNs
Authors: N Venkateswara Rao , Krishna B. T.
Published: October 2024

Automatic modulation classification (AMC) is explained as accurately identifying a modulation of a received signal. AMC systems are a significant component of cognitive radio network (CRN) systems. It is difficult to perform modulation classification on an unsettled radio signal without any previous knowledge of the signal's properties. In this work, the deep learning‐aided AMC is suggested to solve the difficulties of the existing models. In the proposed approach, the modulation classification is attained by performing two steps: (a) data collection and (b) classification. Initially, the required data related to the cognitive environment is collected from online resources. Later, the garnered data are passed to the classification phase. The AMC is performed by the adaptive and dilated hybrid network (ADHN), which is the combination of a temporal convolution network (TCN) and a gated recurrent unit (GRU). The ADHN accurately classifies the modulation even in a noisy environment. The classification performance of the ADHN is further boosted by tuning the parameters of this network via the enriched remora optimization algorithm (EROA). This proposed modulation classification model is suitable for various channels. The comparative validation is performed to ensure the usefulness of the designed system via several measures. By experimental analysis, the proposed system acquires the high value of accuracy, precision, and f1‐score by 94.2, 80.2, and 86.7, respectively, when compared with classical approaches. In addition to this, other metrics are considered and obtained with more true value and less false value. Thus, it ensures the effectiveness of classifying the modulation types in CRNs.
A Sensing and Tunable Two‐Element MIMO Unified Five‐Antenna via Circuit Model for WLAN Cognitive Radio
Authors: Vattiprolu Sandeep Kiran , Nella Anveshkumar
Published: November 2024

This paper presents a five‐element antennas system formed by integrating one sensing and four reconfigurable communicating antennas on a single substrate for cognitive radio applications in the 2.4 and 5 GHz WLAN bands. The five antennas are termed as A‐1, A‐2, A‐3, A‐4, and A‐5, where A‐1 is designed to sense in the 2.4 (2.4–2.484 GHz) and 5 GHz (5.15–5.875) bands. Antenna A‐2, exhibiting two‐element MIMO configuration with A‐3, is designed to communicate in the 5 GHz band, whereas Antenna A‐4, also exhibiting two‐element MIMO configuration with A‐5, operates in the 2.4 GHz band. Each communicating antenna is incorporated with a varactor diode to accomplish continuous frequency tuning operations. Simulated maximum peak gains of A‐1, A‐2, and A‐4 are 7.07, 2.65, and 2.15 dBi, respectively. A good mutual coupling, of less than −15 dB, is noted between the sensing and communicating antennas. MIMO diversity parameters are found to be ECC ≤ 0.01, TARC ≤ −10 dB, DG ≤ 10 dB, and CCL ≤ 0.4. Overall dimensions of the proposed structure are 80 mm × 100 mm × 1.2 mm. The antenna lumped element circuit models developed in ADS software also present good matching with EM simulation. A prototype of the proposed antenna system is fabricated to validate the simulation results. Because the proposed antenna can sense the WLAN bands using the dual‐band antenna (A‐1) and can be able to communicate at the identified spectrum holes using the reconfigurable NB antennas (A‐2 to A‐5), this antenna system is an appropriate module for the cognitive radio applications in WLAN bands.