bluuebunny/crossref_metadata_2025_split huggingface dataset:
Catalytic Atroposelective Synthesis of C−N Axially Chiral Aminophosphines via Dynamic Kinetic Resolution
Authors: Rodríguez‐Franco Carlos , Roldán‐Molina Esther , Aguirre‐Medina Alberto , Fernández Rosario , Hornillos Valentín , Lassaletta José M. 
Published: June 2024

AbstractA ruthenium‐catalyzed reductive amination via asymmetric transfer hydrogenation (ATH) has been used to perform an efficient dynamic kinetic resolution (DKR) of N‐aryl 2‐formyl pyrroles decorated with a phosphine moiety positioned at the ortho’ position. The strategy relies on the labilization of the stereogenic axis in the substrate facilitated by a transient Lewis acid‐base interaction (LABI) between the carbonyl carbon and the phosphorus center. The reaction features broad substrate scope of aliphatic amines and N‐aryl pyrrole scaffolds, and proceeds under very mild conditions to afford P,N atropisomers in good to high yields and excellent enantioselectivities (up to 99 % ee) for both diphenyl and dicyclohexylphosphino derivatives.
Formal High‐Order Cycloadditions of Donor‐Acceptor Cyclopropanes with Cycloheptatrienes
Authors: Borisov Denis D. , Platonov Dmitry N. , Sokolov Nikita A. , Novikov Roman A. , Tomilov Yury V. 
Published: June 2024

AbstractThe design of various cycloaddition/annulation processes is one of the most intriguing challenges in the development of donor‐acceptor (D–A) cyclopropane chemistry. In this work, a new class of formal high‐order [6+n]‐cycloaddition and annulation processes of D–A cyclopropanes with cycloheptatriene systems has been designed and reported, to fill a significant gap in the chemistry of D–A cyclopropanes. The reactivity of methylated cycloheptatrienes from Me1 to Me5 as well as unsubstituted cycloheptatriene was studied in detail under GaCl3 activation conditions, which makes it possible to efficiently generate gallium 1,2‐zwitterionic complexes or 1,3‐zwitterionic intermediates starting from D–A cyclopropanes, while other Lewis acids are ineffective and non‐selective. New examples of formal [6+2]‐, [6+3]‐, [6+4]‐, [6+1]‐, and [4+2]‐cycloaddition and annulation reactions with cycloheptatrienes along with more complex processes were discovered. Cycloheptatriene itself can also successfully act as a hydride anion donor, which allows the ionic hydrogenation of D–A cyclopropanes to be performed under mild conditions. As a result, a number of efficient and highly diastereoselective protocols for the synthesis of seven‐membered carbocycles has been developed.
Anchoring Cs+ Ions on Carbon Vacancies for Selective CO2 Electroreduction to CO at High Current Densities in Membrane Electrode Assembly Electrolyzers
Authors: Sun Yanhui , Chen Junxiang , Du XueMei , Cui Jiwei , Chen Xin , Wu Chenhe , Yang Xinmin , Liu Lequan , Ye Jinhua 
Published: June 2024

AbstractElectrolyte cations have been demonstrated to effectively enhance the rate and selectivity of the electrochemical CO2 reduction reaction (CO2RR), yet their implementation in electrolyte‐free membrane electrode assembly (MEA) electrolyzer presents significant challenges. Herein, an anchored cation strategy that immobilizes Cs+ on carbon vacancies was designed and innovatively implemented in MEA electrolyzer, enabling highly efficient CO2 electroreduction over commercial silver catalyst. Our approach achieves a CO partial current density of approximately 500 mA cm−2 in the MEA electrolyzer, three‐fold enhancement compared to pure Ag. In situ Raman and theoretical analyses, combined with machine learning potentials, reveal anchored Cs induces an electric field that significantly promotes the adsorption of *CO2− intermediates through performing muti‐point energy calculations on each structure. Furthermore, reduced adsorption of *OH intermediates effectively hampers competing hydrogen evolution reaction, as clarified by disk electrode experiments and density functional theory studies. Additionally, coupling our system with commercial polysilicon solar cells yields a notable solar‐to‐CO energy conversion efficiency of 8.3 %. This study opens a new avenue for developing effective cation‐promoting strategy in MEA reactors for efficient CO2RR.
Harnessing Cooperative Multivalency in Thioguanine for Surface‐Enhanced Raman Scattering (SERS)‐Based Differentiation of Polyfunctional Analytes Differing by a Single Functional Group
Authors: Nguyen Lam Bang Thanh , Tan Emily Xi , Leong Shi Xuan , Koh Charlynn Sher Lin , Madhumita Murugan , Phang In Yee , Ling Xing Yi 
Published: June 2024

AbstractSmall‐molecule receptors are increasingly employed to probe various functional groups for (bio)chemical analysis. However, differentiation of polyfunctional analogs sharing multiple functional groups remains challenging for conventional mono‐ and bidentate receptors because their insufficient number of binding sites limits interactions with the least reactive yet property‐determining functional group. Herein, we introduce 6‐thioguanine (TG) as a supramolecular receptor for unique tridentate receptor‐analyte complexation, achieving ≥97 % identification accuracy among 16 polyfunctional analogs across three classes: glycerol derivatives, disubstituted propane, and vicinal diols. Crucially, we demonstrate distinct spectral changes induced by the tridentate interaction between TG's three anchoring points and all the analyte's functional groups, even the least reactive ones. Notably, hydrogen bond (H‐bond) networks formed in the TG‐analyte complexes demonstrate additive effects in binding strength originating from good bond linearity, cooperativity, and resonance, thus strengthening complexation events and amplifying the differences in spectral changes induced among analytes. It also enhances spectral consistency by selectively forming a sole configuration that is stronger than the respective analyte‐analyte interaction. Finally, we achieve 95.4 % accuracy for multiplex identification of a mixture consisting of multiple polyfunctional analogs. We envisage that extension to other multidentate non‐covalent interactions enables the development of interference‐free small molecule‐based sensors for various (bio)chemical analysis applications.
Closed‐Loop Recyclable and Totally Renewable Liquid Crystal Networks with Room‐Temperature Programmability and Reconfigurable Functionalities
Authors: Zhang Chenxuan , Zhang Zhuoqiang , Liu Xiaokong 
Published: June 2024

AbstractDynamic covalent liquid crystal networks (DCv‐LCNs) with straightforward (re)programmability, reprocessability, and recyclability facilitates the manufacture of sophisticated LCN actuators and intelligent robots. However, the DCv‐LCNs are still limited to heat‐assisted programming and polymer‐to‐polymer reprocessing/recycling, which inevitably lead to deterioration of the LCN structures and the actuation performances after repeated programming/processing treatments, owing to the thermal degradation of the polymer network and/or external agent interference. Here, a totally renewable azobenzene‐based DCv‐LCN with room‐temperature programmability and polymer‐to‐monomers chemical recyclability is reported, which was synthesized by crosslinking the azobenzene‐containing dibenzaldehyde monomer and the triamine monomer via the dynamic and dissociable imine bonds. Thanks to the water‐activated dynamics of the imine bonds, the resultant DCv‐LCN can be simply programmed, upon water‐soaking at room temperature, to yield a UV/Vis light‐driven actuator. Importantly, the reported DCv‐LCN undergoes depolymerization in an acid‐solvent medium at room temperature because of the acid‐catalyzed hydrolysis of the imine bonds, giving rise to easy separation and recovery of both monomers in high purity, even with tolerance to additives. The recovered pure monomers can be used to regenerate totally new DCv‐LCNs and actuators, and their functionalities can be reconfigured by removing old and introducing new additives, by implementing the closed‐loop polymer‐monomers‐polymer recycling.
Clinical Issues — July 2024
Authors: Seeman Kristyn , Caso Jamie 
Published: June 2024

THIS MONTH
Cleaning surgical instruments after use in a procedure involving chemotherapeutic medications
Key words: deactivation, decontamination, cleaning, disinfection, chemotherapeutic medication.
Paper count sheets sterilized inside instrument sets
Key words: count sheets, instrument sets, printer ink, toner, toxicity.
Off‐label use of dental devices during direct laryngoscopy
Key words: mouth guard, dental injury, direct laryngoscopy, anesthesia, intubation.
Using intermittent pneumatic compression devices on patients in lithotomy position
Key words: mechanical compression devices, compartment syndrome, lithotomy, venous thromboembolism, thromboprophylaxis.
MEK1/2‐ and ERK1/2‐Mediated Lung Endothelial Injury and Altered Hemostasis Promote Diffuse Alveolar Hemorrhage in Murine Lupus
Authors: Zhuang Haoyang , Han Shuhong , Harris Neil S. , Reeves Westley H. 
Published: June 2024

ObjectiveAbout 3% of patients with lupus develop severe diffuse alveolar hemorrhage (DAH) with pulmonary vasculitis. C57BL/6 (B6) mice with pristane‐induced lupus also develop DAH, but BALB/c mice are resistant. DAH is independent of Toll‐like receptor signaling and other inflammatory pathways. This study examined the role of the MEK1/2 pathway (MEK1/2–ERK1/2, JNK, p38).MethodsB6 and BALB/c mice were treated with pristane with or without inhibitors of MEK1/2 (trametinib/GSK1120212 [GSK]), ERK1/2 (SCH772984 [SCH]), JNK, or p38. Effects on lung hemorrhage and hemostasis were determined.ResultsGSK and SCH abolished DAH, whereas JNK and p38 inhibitors were ineffective. Apoptotic cells were present in lung samples from pristane‐treated mice but not in mice receiving pristane and GSK, and endothelial dysfunction was normalized. Expression of the ERK1/2‐regulated transcription factor early growth response 1 increased in pristane‐treated B6, but not BALB/c, mice and was normalized by GSK. Pristane also increased expression of the anticoagulant genes Tfpi and Thbd in B6 mice. The ratio of Tfpi to tissue factor (F3) to Tfpi increased in B6 (but not BALB/c) mice and was normalized by GSK. Circulating thrombomodulin protein levels increased in B6 mice and returned to normal after GSK treatment. Consistent with augmented endothelial anticoagulant activity, pristane treatment increased tail bleeding in B6 mice.ConclusionPristane treatment promotes lung endothelial injury and DAH in B6 mice by activating the MEK1/2–ERK1/2 pathway and impairing hemostasis. The hereditary factors determining susceptibility to lung injury and bleeding in pristane‐induced lupus are relevant to the pathophysiology of life‐threatening DAH in systemic lupus erythematosus and may help to optimize therapy.
Observer‐based adaptive time‐varying bipartite formation tracking of multi‐agent systems with multiple nonautonomous leaders
Authors: Wei Ge , Wu Jie , Zhan Xisheng , Wu Bo , Yan Huaicheng 
Published: June 2024

AbstractIn this article, the problem of bipartite time‐varying formation (BTVF) tracking for multi‐agent systems (MASs) under signed digraphs is investigated, in which the inputs of leaders are unknown and bounded. A novel kind of adaptive nonsmooth BTVF tracking protocol for MASs is proposed that did not utilize eigenvalue of Laplacian matrix. Based on the state observer, the problem that the system states are not measurable is solved. In addition, in order to avoid undesirable chattering caused by leaders' nonzero inputs, continuous protocols are proposed. And in this case, the error is uniformly ultimately bounded. Lyapunov method reflects the convergence analysis of the submitted protocols. At last, the desired theoretical results are achieved on a multirobot system.
Synthesis, structural, and optical behavior of erbium‐doped silicophosphate glasses for photonics applications
Authors: Bouabdalli El Mahdi , El Jouad Mohamed , Touhtouh Samira , Chellakhi Abdelkhalek , Hajjaji Abdelowahed 
Published: June 2024

AbstractErbium‐incorporated silicophosphate glasses are very desirable in principal sectors such as photonics, optoelectronics, lasers, and illuminating diodes. The focus of the current investigation has been on determining how the erbium dopant affects the optical, physical, and structural characteristics of the silicophosphate‐based glasses. The pure silicophosphate glasses and doped with various contents of erbium were prepared by the sol–gel process in this work. The noncrystalline character of the glasses synthesized was confirmed by the XRD patterns that were obtained. The optical measurement showed that the addition of trivalent erbium ions resulted in an increase in the refractive index of the samples and a decrease in their energy band gap values. It demonstrated the presence of P–O–P linkage stretching vibration modes that were both symmetrical and asymmetrical, P–O in PO4 bending vibration modes, OH group elongating and flexure vibrations, and P–O–H water absorption in glasses. The theoretical values of the optical basicity (Ʌth) increased from 0.465 to 0.472, while the values of the interaction parameter (A) decreased from 0.218 to 0.214 . Silicophosphate glasses doped with trivalent erbium ions show promise as optoelectronic and optical filter system materials.
Novel benzothiazole–pyrazoline–styrene hybrid for ultrasensitive detection of Hg(II) ions: Synthesis and chemosensor evaluation
Authors: Ratnawati Devi , Kartini Indriana , Pranowo Harno Dwi , Kurniawan Yehezkiel Steven , Wahyuningsih Tutik Dwi 
Published: June 2024

AbstractWater pollution has become a serious issue, and mercury(II) ion (Hg(II)) is highly toxic even at low concentrations. Therefore, Hg(II) concentration should be strictly monitored. This study evaluated pyrazoline compounds as fluorescence chemosensor agents for Hg(II) detection. These compounds were prepared from vanillin via etherification, Claisen–Schmidt, and cyclocondensation reactions, to yield benzothiazole–pyrazoline–styrene hybrid compounds. The hybrid compound without styrene was successfully synthesized in 97.70% yield with limit of detection (LoD) and limit of quantification (LoQ) values of 323.5 and 1078 μM, respectively. Conversely, the hybrid compound was produced in 97.29% yield with the LoD and LoQ values of 8.94 and 29.79 nM, respectively. Further spectroscopic investigations revealed that Hg(II) ions can either chelate with three nitrogen of pyridine, pyrazoline, and benzothiazole structures or two oxygen of vanillin and styrene. Furthermore, the hybrid compound was successfully applied in the direct quantification of Hg(II) ions in tap and underground water samples with a validity of 91.63% and 86.08%, respectively, compared with mercury analyzer measurement. The regeneration of pyrazoline was also easily achieved via the addition of an ethylenediaminetetraacetic acid solution. These findings show the promising application of the benzothiazole–pyrazoline–styrene hybrid compound for Hg(II) monitoring in real environmental samples.
Improvement of TaC9‐ABE mediated correction of human SMN2 gene
Authors: Peng Xiaohua , Chi Yue , Wang Jinling , Li Shuangpeng , Liu Yang , Tang Chengcheng , Zhou Xiaoqing , Lu Xuan , Gao Yue , Lai Liangxue , Chen Min , Zou Qingjian 
Published: June 2024

AbstractSpinal muscular atrophy (SMA) is a devastating neuromuscular disease caused by mutations in the survival motor neuron 1 (SMN1) gene. Gene editing technology repairs the conversion of the 6th base T to C in exon 7 of the paralogous SMN2 gene, compensating for the SMN protein expression and promoting the survival and function of motor neurons. However, low editing efficiency and unintended off‐target effects limit the application of this technology. Here, we optimized a TaC9‐adenine base editor (ABE) system by combining Cas9 nickase with the transcription activator‐like effector (TALE)‐adenosine deaminase fusion protein to effectively and precisely edit SMN2 without detectable Cas9 dependent off‐target effects in human cell lines. We also generated human SMA‐induced pluripotent stem cells (SMA‐iPSCs) through the mutation of the splice acceptor or deletion of the exon 7 of SMN1. TaC9‐R10 induced 45% SMN2 T6 > C conversion in the SMA‐iPSCs. The SMN2 T6 > C splice‐corrected SMA‐iPSCs were directionally differentiated into motor neurons, exhibiting SMN protein recovery and antiapoptosis ability. Therefore, the TaC9‐ABE system with dual guides from the combination of Cas9 with TALE could be a potential therapeutic strategy for SMA with high efficacy and safety.
Radiomic score for lung nodules as a prognostic biomarker in locally advanced rectal cancer patients: A bi‐institutional study
Authors: Zhang Zhiyuan , Wang Jiazhou , Dai Di , Xia Fan , Sun Yiqun , Li Guichao , Wan Juefeng , Shen Lijun , Zhang Hui , Wang Yan , Zhong Jie , Bao Jun , Zhang Zhen 
Published: June 2024

AbstractBackgroundUndetermined lung nodules are common in locally advanced rectal cancer (LARC) and lack precise risk stratification. This study aimed to develop a radiomic‐based score (Rad‐score) to distinguish metastasis and predict overall survival (OS) in patients with LARC and lung nodules.MethodsRetrospective data from two institutions (July 10, 2006—September 24, 2015) was used to develop and validate the Rad‐score for distinguishing lung nodule malignancy. The prognostic value of the Rad‐score was investigated in LARC cohorts, leading to the construction and validation of a clinical and radiomic score (Cli‐Rad‐score) that incorporates both clinical and radiomic information for the purpose of improving personalized clinical prognosis prediction. Descriptive statistics, survival analysis, and model comparison were performed to assess the results.ResultsThe Rad‐score demonstrated great performance in distinguishing malignancy, with C‐index values of 0.793 [95% CI: 0.729–0.856] in the training set and 0.730 [95% CI: 0.666–0.874] in the validation set. In independent LARC cohorts, Rad‐score validation achieved C‐index values of 0.794 [95% CI: 0.737–0.851] and 0.747 [95% CI: 0.615–0.879]. Regarding prognostic prediction, Rad‐score effectively stratified patients. Cli‐Rad‐score outperformed the clinicopathological information alone in risk stratification, as evidenced by significantly higher C‐index values (0.735 vs. 0.695 in the internal set and 0.618 vs. 0.595 in the external set).ConclusionsCT‐based radiomics could serve as a reliable and powerful tool for lung nodule malignancy distinction and prognostic prediction in LARC patients. Rad‐score predicts prognosis independently. Incorporation of Cli‐Rad‐score significantly enhances the persionalized clinical prognostic capacity in LARC patients with lung nodules.
Challenges and perspectives in use of artificial intelligence to support treatment recommendations in clinical oncology
Authors: Duwe Gregor , Mercier Dominique , Wiesmann Crispin , Kauth Verena , Moench Kerstin , Junker Markus , Neumann Christopher C. M. , Haferkamp Axel , Dengel Andreas , Höfner Thomas 
Published: June 2024

AbstractArtificial intelligence (AI) promises to be the next revolutionary step in modern society. Yet, its role in all fields of industry and science need to be determined. One very promising field is represented by AI‐based decision‐making tools in clinical oncology leading to more comprehensive, personalized therapy approaches. In this review, the authors provide an overview on all relevant technical applications of AI in oncology, which are required to understand the future challenges and realistic perspectives for decision‐making tools. In recent years, various applications of AI in medicine have been developed focusing on the analysis of radiological and pathological images. AI applications encompass large amounts of complex data supporting clinical decision‐making and reducing errors by objectively quantifying all aspects of the data collected. In clinical oncology, almost all patients receive a treatment recommendation in a multidisciplinary cancer conference at the beginning and during their treatment periods. These highly complex decisions are based on a large amount of information (of the patients and of the various treatment options), which need to be analyzed and correctly classified in a short time. In this review, the authors describe the technical and medical requirements of AI to address these scientific challenges in a multidisciplinary manner. Major challenges in the use of AI in oncology and decision‐making tools are data security, data representation, and explainability of AI‐based outcome predictions, in particular for decision‐making processes in multidisciplinary cancer conferences. Finally, limitations and potential solutions are described and compared for current and future research attempts.
Developing a minimum data standard for student mental health services in the UK: A qualitative study with staff from university support services
Authors: O'Donnell Jennifer , Broglia Emma , Turner Afra , Fudge Mark , Knowles Louise , Barkham Michael ,   SCORE Consortium
Published: June 2024

AbstractObjectiveThis study is part of the Student Counselling Outcomes Research and Evaluation (SCORE) initiative that is pooling university counselling service data to improve datasets and evidence for counselling in this sector. This study aimed to explore university counselling staff views about which data should be included in a national minimum data standard (MDS) to provide evidence for counselling in the sector.MethodSemi‐structured focus groups were conducted with university counselling staff including counsellors, service leaders and mental health advisors. They explored data to include in an MDS, current data collection practices, service and sector level data collection barriers. Two researchers performed content analysis involving identifying fields for inclusion. Thematic analysis was used to identify contextual issues surrounding data collection. Ten focus groups were conducted with 41 participants across 26 university counselling services.ResultsContent analysis identified fields of information for the MDS within the categories of student characteristics, demographics, clinical assessment and service evaluation. Thematic analysis explored context and culture surrounding data collection, barriers and facilitators, institutional influence and ideal data collection practices. This highlights the need for service support and training around data collection, clear processes, and adequate IT infrastructure and staff resources.DiscussionThese findings will inform the development of an MDS as part of the SCORE study. The next stage will involve further development of the MDS and piloting in services. The longer term aim is to implement an MDS across university counselling services, enabling the growth of evidence for the sector which may allow increased funding and service provision.