bluuebunny/crossref_metadata_2025_split huggingface dataset:
Geochemical and Documentary Topography of a Medieval Silver Valley: Detection of Workshops and Identification of Their Function
Authors: Tomczyk Céline , Bernat Alain , Belmon Jérôme , Larousse Nicolas Minvielle 
Published: October 2024

ABSTRACTThis paper presents the interdisciplinary investigation (archaeology, geochemistry, history) of a medieval silver and lead production site located in southern France, in the Minier valley (Occitanie, Aveyron, Le‐Viala‐du‐Tarn). In order to identify the production sites, in situ geochemical surveys were carried out using a portable X‐ray fluorescence spectrometer and differential GPS, guided on the analysis of medieval archival sources. The cartographic representation of the metal concentrations in the surface horizons shows significant enrichment of zinc and lead in the vicinity of the mines. This first type of enrichment makes it possible to highlight the activities of separation of sphalerite and silver‐bearing galena. The galena thus isolated on the hillsides is then transported to the vicinity of watercourses, where it is crushed, washed, and smelted. These secondary activities result in a last type of enrichment in which only lead is found in large quantities. The cross‐referencing of the information made it possible to overcome the challenges related to the location of the mineral processing workshops, which were often invisible on the surface. The medieval workshops have been located and a function suggested, outlining the first trends in the spatial and social division of labour and providing a solid corpus for future archaeological excavations. Finally, this study highlights the persistence of significant metal contamination in the soils of a rural valley and encourages the consideration of former mining areas when examining the environmental impact of metal production.
Hybrid trajectory tracking control of wheeled mobile robots using predictive kinematic control and dynamic robust control
Authors: Kordi Fahimeh , Mobayen Saleh , Rezaalikhani Hamidreza , Nikoukar Javad 
Published: October 2024

AbstractTrajectory tracking control of wheeled mobile robots (WMRs) is still a remarkable problem for many applications. In the present paper, a hybrid control is presented based on dynamic and kinematic equations of motion for wheeled mobile robots in the presence of the sum of the external disturbances and parametric uncertainty. The designed control for the WMR utilizes control and guidance to reach the reference path. In many studies, a control strategy is normally employed for WMR. However, in this study, hybrid control was used for the mentioned purpose. Akin to other studies, the kinematic control scheme here was based on the predictive control, and the dynamic control scheme was designed based on the robust control. Therefore, in this article, having introduced the kinematic model, a nonlinear predictive control was proved and designed. In the next step, a finite‐time integral type terminal sliding mode control (FITSMC) was designed based on the nonlinear dynamic model in order to automatically adjust the control gain and eliminate online disturbances and destructive chattering phenomena completely. In particular, a finite‐time disturbance observer was designed to estimate the external disturbances. The proof of the new proposed control scheme was presented using Lyapunov stability theory and numerical results. The mentioned integrated scheme, including predictive control (outer loop) and nonlinear adaptive control (inner loop), ensures the convergence and optimal tracking performance of all signals, as a result of which the tracking errors can arbitrarily converge to the origin in a finite time. In the final step, the simulation results were presented to show the effectiveness of the proposed scheme using MATLAB software, and the introduced control design was compared with a similar controller quantitatively and qualitatively.
Characterization and Degradation of Triphenylmethane Dyes and Their Leuco‐Derivatives by Heterologously Expressed Laccase From Coprinus cinerea
Authors: Qian Cen , Pei Zuodi , Wang Bo , Peng Rihe , Yao Quanhong 
Published: October 2024

ABSTRACTLaccase is a copper‐containing polyphenol oxidase that can oxidize phenolic and non‐phenolic organic substrates. In the past decades, laccases had received considerable attention because of the ability to degrade various organic substances. Based on the codon preference of the Pichia pastoris expression system, this study optimized the gene structure of the laccase gene Lcc1 from Coprius cinerea through synthetic biology methods. A new gene Lcc1I was synthesized and heterologously expressed in P. pastoris. After 3 days of cultivation in a shake flask at 30°C, the transformants produced at a yield of 890 mg L−1protein. The highest production level of the recombinant laccase was 2760 U L−1. The molecular mass of the recombinant laccase was estimated at 60 kDa. The enzyme showed highest activity at pH 3.4 and 45°C. It possessed better stability at higher pH and lower temperature condition. Using 2,2'‐azino‐bis‐(3‐ethylbenzothiazoline)−6‐sulphonate (ABTS) as the substrate, the Km and Vmax values were 0.136 mM and 9778 μM min−1 mg−1, respectively. The recombinant laccase could directly oxidize some triphenylmethane dyes like leuco‐crystal violet (LCV) and leuco‐malachite green (LMG). With the help of ABTS mediator, it could oxidize and degrade 77.7% crystal violet (CV) and 79.2% malachite green (MG) within 1 h. Our results indicate that optimization of the laccase gene achieves good expression results in the host system. The dye degradation model constructed in this study may also be applied to the degradation of other organic pollutants and toxic substances, providing new solutions for environmental remediation against the increasingly severe environmental pollution.
Improving CsOAC Activity in Saccharomyces cerevisiae for Directed Production of Olivetolic Acid through Rational Design
Authors: Spitzer Saskia , Aras Marco , Kayser Oliver 
Published: October 2024

AbstractOlivetolic acid (OA) is an essential precursor in the cannabinoid biosynthesis. It is produced through a unique interaction between the two proteins, olivetol synthase (CsOLS) and olivetolic acid cyclase (CsOAC). When the OA biosynthesis is transferred to Saccharomyces cerevisiae, olivetol (OL) is produced as a side product, even with a high enhancement of copy number of CsOAC. In order to increase the OA titer while decreasing the OL titer in S. cerevisiae, rational design was applied to CsOAC using in silico approaches such as protein‐ligand docking to find potential protein variants. In vivo screening and also testing different approaches for both proteins was applied to identify the best performing variants of CsOAC. Four variants were identified that gave the desired properties. The best CsOAC variant, G82 A/L92Y, resulted in a 1.7‐fold increase in OA production and a shift in the ratio between the two products towards OA.
Modular Access to Chiral 1,3‐Substituted Fragments via Nickel‐Catalyzed Arylboration Reaction†
Authors: Bao Yang , Yao Tong , Kong Weiyu , Li Yangyang , Fu Ying , Wu Dong , Yin Guoyin 
Published: October 2024

Comprehensive SummaryChiral 1,3‐substituted fragments are ubiquitous in pharmaceutical molecules and natural products, prompting the development of numerous methods to access these structures. Nonetheless, devising synthetic routes for complex chiral architectures in practical applications typically demands years of expertise. Herein, we developed a nickel‐catalyzed enantioselective migratory arylboration reaction of allylboronic esters using a chiral 1,2‐diamine ligand, yielding a range of chiral 1,3‐bis(boronates) with high enantioselectivity. The protocol is characterized by its use of commercially available substrates, mild reaction conditions, user‐friendly procedures, and a broad substrate compatibility. Moreover, we demonstrate the practicality and application potential of this reaction by synthesizing several key drug intermediates.
Catalytic Asymmetric Conjugate Addition and Allylic Substitution of Cyclobutenones with Arylzinc Halides
Authors: Pan Renming , Lu Ping 
Published: October 2024

Comprehensive SummaryConjugate addition and allylic substitution are two essential chemical transformations, and they could be competitive for substrates with multiple reactive sites. Herein, we report the diversified enantioselective synthesis of cyclobutenes via the functionalization of cyclobutenones. The conjugate addition of cyclobutenones with arylzinc halides provided enantioenriched cyclobutenes with all‐carbon quaternary centers. On the other hand, when cyclobutenones with gem‐dichloro groups were employed, a chemo‐ and enantioselective allylic substitution occurred. Further synthetic utility was demonstrated for synthesizing versatile cyclobutane derivatives, together with ring‐opening and expansion products.
Phase 2 trial of avelumab in combination with gemcitabine in advanced leiomyosarcoma as a second‐line treatment (EAGLES, Korean Cancer Study Group UN18‐09)
Authors: Kim Miso , Kim Yu Jung , Suh Koung Jin , Kim Se Hyun , Kim Jeong Eun , Jeong Juhyeon , Hong Jung Yong , Lee Jeeyun , Lee Su Jin , Oh Sung Yong , Kim Jung Hoon , Lee Gyeong‐Won , Ahn Mi Sun , Choi Wonyoung , Choi Yoon Ji , Lee Taebum , Oum Chiyoon , Kim Jeongkyu , Kim Young Saing , Ahn Jin‐Hee 
Published: October 2024

AbstractBackgroundIn this single‐arm, multicenter, phase 2 trial, the authors evaluated the efficacy and safety of avelumab plus gemcitabine in patients with leiomyosarcoma (LMS) who failed on first‐line chemotherapy.MethodsPatients with advanced LMS received avelumab 10 mg/kg on days 1 and 15 (for up to 24 months) plus gemcitabine 1000 mg/m2 on days 1, 8, and 15 of a 28‐day cycle until they developed disease progression or intolerable toxicity. The primary end point was the objective response rate (ORR).ResultsIn total, 38 patients were enrolled. Of these, 35 patients were evaluable, and the ORR was 20% (95% confidence interval; [CI], 8%–37%). The disease control rate was 71%, and the median duration of response was 21.8 months (range, 7.6 to ≥43.3 months). The median progression free‐survival was 5.6 months (95% CI, 4.5–6.8 months), and the median overall survival was 27.5 months (95% CI, 20.4–34.6 months). Grade 3–4 adverse events occurred in 70% of patients, of which neutropenia was the most common (54%). Immune‐mediated adverse events occurred in five patients (14%; hypothyroidism, n = 3; hepatitis, n = 2). Patients who had a higher density of tumor‐infiltrating lymphocytes (greater than the median) exhibited better ORR (35% vs. 8%; p = .104), progression‐free survival (median, 7.3 vs. 3.3 months; p = .024), and overall survival (median, not reached vs. 21.5 months; p = .027).ConclusionsThe combination of avelumab and gemcitabine demonstrated promising efficacy and manageable safety in patients with advanced LMS who progressed on first‐line therapy. Tumor‐infiltrating lymphocyte density may be an important factor in predicting the response to combining immunotherapy with chemotherapy.
Validity and Reliability of the Amharic Version of EORTC QLQ‐OG25 Among Esophagogastric Cancer Patients in Ethiopia
Authors: Abebe Lidya Genene , Wondimagegnehu Abigiya , Kantelhardt Eva Johanna , Addissie Adamu 
Published: October 2024

ABSTRACTBackgroundCancers of the stomach and esophagus are the fourth and sixth most common causes of cancer‐related deaths worldwide, respectively. Although various tools have been developed to assess the quality of life of patients with esophagogastric cancer, EORTC QLQ‐C30 and EORTC QLQ‐OG25 are the most used all over the world. However, they have not been validated in an Ethiopian context. Therefore, this study aimed to evaluate the psychometric properties of EORTC QLQ‐OG25 among Ethiopian patients with esophageal and gastric cancer.MethodsEORTC QLQ‐OG25 is a 25‐item tool with 10 single items and six symptom scales: Eating restrictions, reflux, dysphagia, odynophagia, discomfort and pain, and anxiety. The tool was translated into Amharic according to the EORTC forward‐backward translation protocol. To check its validity and reliability, a cross‐sectional study among 158 patients was conducted from March to May 2020 at Tikur Anbessa Specialized Hospital, Addis Ababa, Ethiopia. The psychometric properties of EORTC QLQ‐C30 and EORTC QLQ‐OG25 were assessed using multitrait scale analysis, known group validity, convergent validity, and divergent validity. Internal consistency was examined with Cronbach's alpha.ResultEighty‐three (52.5%) of the participants were men; the median age was 50 years (IQR = 18 years). The overall item correlation alpha values ranged between 0.39 and 0.7. All item correlations within their scales were greater than 0.4. The correlation coefficients between all items and their own domain were greater than for other domains. The esophagogastric and core questionnaire correlation ranged from −0.65 to 0.62. The tool showed a significant difference between patients with good physical function and those with impaired physical function.ConclusionsThe findings suggest that the Amharic version of EORTC QLQ‐OG25 is a valid and reliable tool among patients from Ethiopia with esophagus and gastric cancer. Therefore, we recommend that researchers and clinicians use the core tool together with the specific tool.
Diatoms in Focus: Chemically Doped Biosilica for Customized Nanomaterials
Authors: Vicente‐Garcia Cesar , Vona Danilo , Flemma Annarita , Cicco Stefania Roberta , Farinola Gianluca Maria 
Published: October 2024

AbstractDiatoms are photosynthetic microalgae widely diffused around the globe and well adapted to thrive in diverse environments. Their success is closely related to the nanostructured biosilica shell (frustule) that serves as exoskeleton. Said structures have attracted great attention, thanks to their hierarchically ordered network of micro‐ and nanopores. Frustules display high specific surface, mechanical resistance and photonic properties, useful for the design of functional and complex materials, with applications including sensing, biomedicine, optoelectronics and energy storage and conversion. Current technology allows to alter the chemical composition of extracted frustules with a diverse array of elements, via chemical and biochemical strategies, without compromising their valuable morphology. We started our research on diatoms from the viewpoint of material scientists, envisaging the possibilities of these nanostructured silica shells as a general platform to obtain functional materials for several applications via chemical functionalization. Our first paper in the field was published in ChemPlusChem ten years ago. Ten years later, in this Perspective, we gather the most recent and relevant functional materials derived from diatom biosilica to show the growth and diversification that this field is currently experiencing, and the key role it will play in the near future.
A Carbon Capture and Utilization Process for the Production of Solid Carbon Materials from Atmospheric CO2 – Part 1: Process Performance
Authors: Uhlenbruck Neele , Pfeifer Peter , Dietrich Benjamin , Hofberger Christoph M. , Krumholz Ralf , Saxler Antonio , Schulz Linus , Stoppel Leonid , Wetzel Thomas 
Published: October 2024

AbstractThe successful operation of a process that converts atmospheric CO2 into solid carbon products is presented as an alternative to fossil based solid carbon production. In a first step, CO2 is removed from the atmosphere by a direct air capture (DAC) unit. The gas is then mixed with hydrogen and enters a methanation unit. Depending on the operation conditions, gas mixtures consisting of mainly methane with either H2 or CO2 as side‐component are obtained. After precipitating the water formed during the methanation step, the remaining gas mixture is fed into a bubble column reactor filled with liquid tin. During the rise of the gas bubbles, methane is thermally split up into hydrogen and solid carbon. The latter is continuously removed from the liquid metal surface as a fine powder by pneumatic conveying. This article is the first of two articles, focusing on the performance of the methanation and methane pyrolysis steps. The experimental results are complemented by thermodynamic analyses and reaction modelling. A detailed analysis of the solid carbon product of the process is presented in the second part.
A Carbon Capture and Utilization Process for the Production of Solid Carbon Materials from Atmospheric CO2 – Part 2: Carbon Characterization
Authors: Uhlenbruck Neele , Dietrich Benjamin , Heißler Stefan , Hofberger Christoph M. , Krumholz Ralf , Stoppel Leonid , Trouillet Vanessa , Weidler Peter G. , Wetzel Thomas 
Published: October 2024

AbstractThis article is the second part of a study reporting the results of a novel carbon capture and utilization (CCU) process, which converts atmospheric CO2 into solid carbon materials. The CCU process combines direct air capture (DAC) with catalytic methanation, which is then followed by methane pyrolysis in a reactor filled with liquid tin. While Part 1 discussed the performance of the overall process and individual process steps regarding conversions and yields, Part 2 characterizes the solid carbon products obtained under various synthesis conditions. The effects of the pyrolysis temperature and the composition of the gas mixture from the methanation step on the solid carbon product are analyzed. Carbon powder is synthesized from methane with either N2, H2 or CO2 as most important impurity. Carbon samples are characterized using SEM, TEM, Raman spectroscopy, XPS and XRD analysis. Very thin, disordered carbon flakes, soot aggregates and large carbon onions are identified as the main solid products of the process. Their formation mechanisms in the liquid metal‐filled pyrolysis reactor are discussed.
Sustainable Formate Production via Highly Active CO2 Hydrogenation Using Porous Organometallic Polymer with Ru‐PNP Active Sites
Authors: Park Hongjin , Park Kwangho , Lee Ung , Yoon Sungho 
Published: October 2024

AbstractEfforts to combine the advantages of homogeneous catalysts in terms of activity with the ease of separation process offered by heterogeneous catalysts continue to be actively pursued in the field of catalyst development. Heterogeneous catalysts were synthesized from Ru‐MACHO organometallic compounds, recognized for their high hydrogenation catalytic activity linked to the active site of the Ru‐PNP motif, through direct polymerization utilizing the Friedel‐Crafts reaction. These catalysts were then applied for the conversion of greenhouse gas carbon dioxide (CO2) into formate via hydrogenation, exhibited with a record‐high turnover frequency of 31,700 and a productivity of 36,100 kgformate/(kgcatalyst ⋅ d). Furthermore, the facile separation characteristics and recyclability of the heterogeneous catalysts were confirmed.
PYCR1 promotes liver cancer cell growth and metastasis by regulating IRS1 expression through lactylation modification
Authors: Wang Haoyu , Xu Mu , Zhang Tong , Pan Jinkun , Li Chaopu , Pan Bei , Zhou Linpeng , Huang Yun , Gao Chenzi , He Mengping , Xue Yao , Ji Xuetao , Zhang Xu , Wang Ning , Zhou Hongwen , Wang Qian , Li John Zhong 
Published: October 2024

AbstractBackgroundLiver cancer (LC) is among the deadliest cancers worldwide, with existing treatments showing limited efficacy. This study aimed to elucidate the role and underlying mechanisms of pyrroline‐5‐carboxylate reductase 1 (PYCR1) as a potential therapeutic target in LC.MethodsImmunohistochemistry and Western blot were used to analyse the expression of PYCR1 in LC cells and tissues. EdU assays, colony‐forming assays, scratch wound healing assays, Transwell assays, nude mouse xenograft models and nude mouse lung metastasis models were used to detect the growth and metastasis abilities of LC cells. Transcriptome sequencing was used to search for downstream target genes regulated by PYCR1, and metabolomics was used to identify the downstream metabolites regulated by PYCR1. ChIP assays were used to analyse the enrichment of H3K18 lactylation in the IRS1 promoter region.ResultsWe found that the expression of PYCR1 was significantly increased in HCC and that this high expression was associated with poor prognosis in HCC patients. Knockout or inhibition of PYCR1 inhibited HCC cell proliferation, migration and invasion both in vivo and in vitro. In addition, we revealed that knocking out or inhibiting PYCR1 could inhibit glycolysis in HCC cells and reduce H3K18 lactylation of the IRS1 histone, thereby inhibiting IRS1 expression.ConclusionsOur findings identify PYCR1 as a pivotal regulator of LC progression that influences tumour cell metabolism and gene expression. By demonstrating the potential of targeting PYCR1 to inhibit LC cell proliferation and metastasis, this study identified PYCR1 as a promising therapeutic target for LC.Highlights
Pyrroline‐5‐carboxylate reductase 1 (PYCR1) promotes the proliferation and metastasis of liver cancer (LC) cells.
The expression of PYCR1 in LC is regulated by DNA methylation.
Knocking down or inhibiting PYCR1 inhibits glycolysis as well as the PI3K/AKT/mTOR and MAPK/ERK pathways in LC cells.
PYCR1 regulates the transcriptional activity of IRS1 by affecting H3K18 lactylation in its promoter region.
Win ratio analysis of transvenous phrenic nerve stimulation to treat central sleep apnoea in heart failure
Authors: Abraham William T. , Oldenburg Olaf , Lainscak Mitja , Khayat Rami , Asin Jerryll , Ponikowski Piotr , Germany Robin , McKane Scott , Costanzo Maria Rosa 
Published: October 2024

AbstractAimsCentral sleep apnoea (CSA) is present in 20–40% of heart failure (HF) patients and is associated with poor clinical outcomes and health status. Transvenous phrenic nerve stimulation (TPNS) is an available treatment for CSA in HF patients. The impact on HF outcomes is incompletely understood. The win ratio (WR) allows inclusion of multiple endpoint components, considers the relative severity of each component, and permits assessment of recurrent events in evaluation of clinical benefit.Methods and resultsA WR hierarchy was pre‐defined for analysis of the HF subgroup of the remedē® System Pivotal Trial. The analysis used three hierarchical components to compare all treated to all control subjects: longest survival, lowest HF hospitalization rate, and ≥2‐category difference in Patient Global Assessment at 6 months. Sensitivity analyses were performed substituting Epworth Sleepiness Scale and 4% oxygen desaturation index for the third component, and a 4‐component WR hierarchy was also evaluated. Ninety‐one HF subjects, 43 receiving TPNS and 48 in the control group, provided 2064 pairwise comparisons. More patients treated with TPNS experienced clinical benefit compared with control (WR 4.92, 95% confidence interval 2.27–10.63, P < 0.0001). There were 1111 (53.83%) winning pairwise comparisons for the treatment group and 226 (10.95%) for the control group. Similarly, large WRs were observed for all additional WR hierarchies.ConclusionsThis WR analysis of the remedē® System Pivotal Trial suggests that TPNS may be superior to untreated CSA in HF patients with CSA using a hierarchical clinical benefit endpoint composed of mortality, HF hospitalization, and health status.