bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stereoselective Reactions Promoted by Alkali Metal Salts of Phosphoric Acid Organocatalysts
Authors: Cocco Emanuele , Antenucci Achille , Carlone Armando , Manini Paola , Pesciaioli Fabio , Dughera Stefano 
Published: April 2024

AbstractThe catalytic application of chiral phosphoric acids (CPAs) from 2004 to date represents a true milestone for asymmetric organocatalysis. However, not only the free acids can be conveniently employed in numerous different asymmetric synthetic methodologies, thus being strictly compliant to the concept of “organocatalysis”, but also their metal salts. This review focuses on asymmetric reactions in which the catalyst is a chiral alkali or alkaline‐earth metal phosphate.
Highly Stereoselective Synthesis of 1,3‐Enynes via Aryl to Vinyl 1,4‐Palladium Migration/Sonogashira Coupling Sequence
Authors: Chen Zheng‐Yu , Ji Xiao‐Ming , Wang Xue , Asgari Motahareh , Fu Jian‐Guo , Zhang Shu‐Sheng , Feng Chen‐Guo 
Published: April 2024

AbstractAlkynylation of alkenyl bromoarenes via aryl to vinyl 1,4‐palladium migration/copper‐free Sonogashira coupling sequence has been developed. This approach provides a facile methodology for the highly stereoselective synthesis of multi‐substituted 1,3‐enynes in good to excellent yields and regioselectivities.
External Electric Field Control of Exciton Motion in Porphyrin‐Based Metal Organic Frameworks
Authors: Singhvi Puja , Vankova Nina , Heine Thomas 
Published: April 2024

AbstractPorphyrins are excellent light‐harvesting complexes. Presently they are unsuitable for photovoltaic applications, as their excellent light absorbance is compensated to a large extent by their poor transport properties, where most excitons are lost by recombination. Arranging porphyrins in regular, strongly bound, lattices of surface‐anchored metal‐organic frameworks (PP‐SURMOFs) may facilitate charge carrier dissociation, but does not significantly enhance the conductive properties. In most cases, photogenerated excitons traverse undirected, Brownian motion through a hopping process, resulting in a substantial diffusion length to reach electrodes, leading to significant exciton loss through recombination. Here, we propose to guide exciton diffusion indirectly by an external electric field. We show that electric fields, even as strong as 1 V nm−1, do not affect the HOMO‐LUMO gap of the porphyrins. However, fields of 0.1 V nm−1 and even less demonstrate a notable Stark effect, with slight band gap reductions, for some PP‐SURMOFs. When applied as an electric field gradient, for instance, via the substrate, it creates a unidirectional hopping pathway for the excitons. Consequently, we expect a significant reduction of exciton diffusion length leading to increased utilization of photogenerated excitons as they reach the electrodes. This strategy holds promise for integrating photoactive molecules in photovoltaic and photocatalytic applications.
Polydentate Amidinato‐Silylenes, ‐Germylenes and ‐Stannylenes
Authors: Cabeza Javier A. , García‐Álvarez Pablo 
Published: April 2024

AbstractThis review article focuses on amidinatotetrylenes that potentially can (or have already shown to) behave as bi‐ or tridentate ligands because they contain at least one amidinatotetrylene moiety (silylene, germylene or stannylene) and one (or more) additional coordinable fragment(s). Currently, they are being widely used as ligands in coordination chemistry, small molecule activation and catalysis. This review classifies those that have been isolated as transition metal‐free compounds into five families that differ in the position(s) of the donor group(s) (D) on the amidinatotetrylene moiety, namely: ED{R1NC(R2)NR1}, EX{DNC(R2)NR1}, EX{R1NC(D)NR1}, EX{DNC(R2)ND} and E{R1NC(R2)ND}2 (E=Si, Ge or Sn). Those that do not exist as transition metal‐free compounds but have been observed as ligands in transition metal complexes are cyclometallated and ring‐opened amidinatotetrylene ligands. This article presents schematic descriptions of their structures, the approaches used for their syntheses and a quick overview of their involvement (as ligands) in transition metal‐catalysed reactions. The literature is covered up to the end of 2023.
Formation, Selective Encapsulation, and Tautomerization Control of Isoindolone Utilizing Guanidinium Sulfonate Frameworks
Authors: Chaudhry Mohammad T. , Newman Justin A. , Lee Alfred Y. 
Published: April 2024

AbstractHerein we report the use of tetrakis (guanidinium) pyrenetetrasulfonate (G4PYR) and bis (guanidinium) 1,5‐napthalene disulfonate (G2NDS) to catalyze the cyclization of 2‐cyanobenzamide (1) to isoindolone (2). Moreover, we demonstrate the remarkable selectivity of these guanidinium organosulfonate hosts in encapsulating 2 over 1. By thoroughly investigating the intramolecular cyclization reaction, we determined that guanidinium and the organosulfonate moiety acts as the catalyst in this process. Additionally, 2 is selectively encapsulated, even in mixtures of other structurally similar heterocycles like indole. Furthermore, the tautomeric state of 2 (amino isoindolone (2–A) and imino isoindolinone forms (2–I)) can be controlled by utilizing different guanidinium organosulfonate frameworks.
Continuous Synthesis of a Macrocyclic Sulfite of Polyethylene Glycol by Cascaded Continuous Stirred Tank Reactors (CSTRs)
Authors: Wei Jichang , Liu Yinli , Sun Yuchen , Bai Jun , Gao He , Yang Zhaojun , Pan Long 
Published: April 2024

AbstractInvited for the cover of this issue is the group of Long Pan and co‐workers at Asymchem Life Sciences (Tianjin) Co. Ltd. The image depicts a novel continuous process for the synthesis of a macrocyclic poly(ethylene glycol) (PEG) sulfite, the precursor to PEG macrocyclic sulfate, a useful building block in PEG chemistry. Read the full text of the article at 10.1002/chem.202304319.
Effect of Aggregation Structure on Capacitive Energy Storage in Conducting Polymer Films
Authors: Li Na , Wang Yeye , Zhao Wendi , Chen Zhihong , Liu Peipei , Zhou Weiqiang , Jiang Fengxing , Liu Congcong , Xu Jingkun 
Published: April 2024

AbstractConducting polymers (CPs), a significant class of electrochemical capacitor electrode materials, exhibit exceptional capacitive energy storage performance in aqueous electrolytes. Current research primarily concentrates on enhancing the electrical conductivity and capacitive performance of CPs via molecular design and structural control. However, the absence of a comprehensive understanding of the impact of molecular chain spatial order on ion/electron transport and capacitive performance impedes the development and optimization of advanced electrode materials. Here, a solvent treatment strategy is employed to modulate the molecular chain spatial order of PEDOT : PSS films. The results of electrochemical performance tests and Grazing Incidence Wide Angle X‐ray Scattering (GIWAXS) show that Poly(3,4‐ethylenedioxythiophene) : poly(styrenesulfonic acid) (PEDOT : PSS) films with both face‐on and edge‐on orientations exhibit exceptional electronic conductivity and ion diffusion efficiency, with capacitive performance 1.33 times higher than that of PEDOT : PSS films with only edge‐on orientation. Consequently, molecular chain orientations conducive to charge transport not only enhance inter‐chain coupling, but also effectively reduce ion transport resistance, enabling efficient capacitive energy storage. This research provides novel insights for the design and development of higher performance CPs‐based electrode materials.
Community responses of arbuscular mycorrhiza fungi to hydrological gradients in a riparian Phragmites australis wetland
Authors: Chen Xue‐dong , Zhu Ying , Feng Mei‐na , Li Ji‐hang , Shi Ming‐yan 
Published: April 2024

AbstractThe hydrological regime is considered to be the major factor that affects the distribution of arbuscular mycorrhiza (AM) fungi in wetlands. We aimed to investigate the responses of AM fungal community to different hydrological gradients. Illumina Miseq sequencing technology was used to study the AM fungal community structure in roots and rhizosphere soils of Phragmites australis in different moisture areas (dry area, alternating wet and dry area, and flooded area) in Mengjin Yellow River wetland. The rhizosphere soils and roots hosted different AM fungal communities. In roots, the AM fungal colonization and Chao1 richness in dry area were significantly higher than that in alternating wet and dry area and flooded area, but the community composition did not vary clearly under different water conditions. In rhizosphere soils, the Chao1 richness of AM fungi in flooded area was significantly higher than that in alternating wet and dry area and dry area, and the AM fungal community structure obviously differed across different areas. The redundancy analyses indicated that changes in the AM fungal community in soils were associated with altered soil properties, and the abundance of the dominant genus Glomus was mostly positively correlated with alkali‐hydrolyzable nitrogen in soils. This study helps us to understand the responses of AM fungal community to hydrological gradients in wetlands.
Patterns, drivers, and implications of postfire delayed tree mortality in temperate conifer forests of the western United States
Authors: Busby Sebastian , Evers Cody , Holz Andrés 
Published: April 2024

AbstractConifer forest resilience may be threatened by increasing wildfire activity and compound disturbances in western North America. Fire refugia enhance forest resilience, yet may decline over time due to delayed mortality—a process that remains poorly understood at landscape and regional scales. To address this uncertainty, we used high‐resolution satellite imagery (5‐m pixel) to map and quantify delayed mortality of conifer tree cover between 1 and 5 years postfire, across 30 large wildfires that burned within three montane ecoregions in the western United States. We used statistical models to explore the influence of burn severity, topography, soils, and climate moisture deficit on delayed mortality. We estimate that delayed mortality reduced live conifer tree cover by 5%–25% at the fire perimeter scale and 12%–15% at the ecoregion scale. Remotely sensed burn severity (1‐year postfire) was the strongest predictor of delayed mortality, indicating patch‐level fire effects are a strong proxy for fire injury severity among surviving trees that eventually perish. Delayed mortality rates were further influenced by long‐term average and short‐term postfire climate moisture deficits, illustrating the impact of drought on fire‐injured tree survival. Our work demonstrates that delayed mortality in conifer forests of the western United States can be remotely quantified at a fine grain and landscape scale, is a spatially extensive phenomenon, is driven by fire–climate–environment interactions, and has important ecological implications.
Rare‐Earth‐Metal Alkyl and Aryl Compounds in Organic Synthesis
Authors: Mortis Alexandros , Anwander Reiner 
Published: April 2024

AbstractRare‐earth‐metal (Ln) alkyl and aryl compounds feature highly reactive, thermally labile [Ln−C] σ‐bonds which result in rapid and violent decomposition in the presence of air and moisture. Nevertheless, such [Ln−C] moieties display important intermediate species in numerous organic transformations. Reagents containing [Ln−C] bonds are deliberately generated in situ like Imamoto‐type reagents Ln(III)Cl3/RLi (routinely at low temperatures) or “heavy” lanthanide‐Grignard compounds RLnX. Samarium(III)‐alkyl species are supposed intermediates of SmI2‐promoted Barbier‐type carbon–carbon coupling reactions. Alkyl/aryl ligand exchange at Ln(III) centers has been identified as the crucial step of lanthanide–halogen‐exchange reactions. In the meantime, several such mixed alkyl/halogenido complexes, devoid of an ancillary ligand, could be isolated and scrutinized with regard to structure and reactivity. More recently, Ln(III)‐alkylidene complexes could be accessed, structurally authenticated and successfully employed in Tebbe‐like olefination reactions of ketones.
Bioactive scaffolds for tissue engineering: A review of decellularized extracellular matrix applications and innovations
Authors: Liu Juan , Song Qingru , Yin Wenzhen , Li Chen , An Ni , Le Yinpeng , Wang Qi , Feng Yutian , Hu Yuelei , Wang Yunfang 
Published: April 2024

AbstractDecellularized extracellular matrix (dECM) offers a three‐dimensional, non‐immunogenic scaffold, enriched with bioactive components, making it a suitable candidate for tissue regeneration. Although dECM‐based scaffolds have been successfully implemented in preclinical and clinical settings within tissue engineering and regenerative medicine, the mechanisms of tissue remodeling and functional restoration are not fully understood. This review critically assesses the state‐of‐the‐art in dECM scaffolds, including decellularization techniques for various tissues, quality control and cross‐linking. It highlights the functional properties of dECM components and their latest applications in multiorgan tissue engineering and biomedicine. Additionally, the review addresses current challenges and limitations of decellularized scaffolds and offers perspectives on future directions in the field.
FGFR1 fusions as a novel molecular driver in rhabdomyosarcoma
Authors: de Traux De Wardin Henry , Cyrta Joanna , Dermawan Josephine K. , Guillemot Delphine , Orbach Daniel , Aerts Isabelle , Pierron Gaelle , Antonescu Cristina R. 
Published: April 2024

AbstractThe wide application of RNA sequencing in clinical practice has allowed the discovery of novel fusion genes, which have contributed to a refined molecular classification of rhabdomyosarcoma (RMS). Most fusions in RMS result in aberrant transcription factors, such as PAX3/7::FOXO1 in alveolar RMS (ARMS) and fusions involving VGLL2 or NCOA2 in infantile spindle cell RMS. However, recurrent fusions driving oncogenic kinase activation have not been reported in RMS. Triggered by an index case of an unclassified RMS (overlapping features between ARMS and sclerosing RMS) with a novel FGFR1::ANK1 fusion, we reviewed our molecular files for cases harboring FGFR1‐related fusions. One additional case with an FGFR1::TACC1 fusion was identified in a tumor resembling embryonal RMS (ERMS) with anaplasia, but with no pathogenic variants in TP53 or DICER1 on germline testing. Both cases occurred in males, aged 7 and 24, and in the pelvis. The 2nd case also harbored additional alterations, including somatic TP53 and TET2 mutations. Two additional RMS cases (one unclassified, one ERMS) with FGFR1 overexpression but lacking FGFR1 fusions were identified by RNA sequencing. These two cases and the FGFR1::TACC1‐positive case clustered together with the ERMS group by RNAseq. This is the first report of RMS harboring recurrent FGFR1 fusions. However, it remains unclear if FGFR1 fusions define a novel subset of RMS or alternatively, whether this alteration can sporadically drive the pathogenesis of known RMS subtypes, such as ERMS. Additional larger series with integrated genomic and epigenetic datasets are needed for better subclassification, as the resulting oncogenic kinase activation underscores the potential for targeted therapy.
Effect of radiation cross‐linked collagen scaffold in alveolar ridge preservation of extraction socket
Authors: Li Hongwei , Yang Chen , Chen Gong , Wang Bozhao , Li Jian , Xu Ling 
Published: April 2024

AbstractThis study aimed to evaluate the properties of radiation cross‐linked collagen scaffold (RCS) and its efficacy for alveolar ridge preservation (ARP). RCS was prepared from collagen dispersion by electron beam irradiation and freeze‐drying. The microstructure, swelling ratio, area alteration and mechanical properties of RCS were characterized. Fifty‐four New Zealand rabbits performing incisor extraction on maxilla and mandible were randomly assigned into positive, sham operation or treatment groups. Micro‐computed tomography (micro‐CT) scans, performed after 1, 4, and 12 weeks of surgery, were to assess changes in ridge height at buccal and palatal side, in ridge width and in micromorphological parameters. Histological analysis accessed socket microarchitecture. The results showed that RCS had stable mechanical properties and morphologic features that provided a reliable physical support for ARP. Dimensional changes in treatment group revealed significantly greater vertical height at buccal (5.32 [3.37, 7.26] mm, p < .0001) and palatal (4.37 [2.66, 6.09] mm, p < .0001) side, and horizontal width at the maxilla (0.16 [0.04, 0.28] mm, p < .01) and mandible (0.33 [0.11, 0.54] mm, p < .01) than those in sham operation group after 12 weeks. The treatment group had advantage than positive group in vertical height preservation, quantitatively. The order and density of bone trabeculae were improved in treatment group. These findings indicated that RCS had the potential to serve as an effective scaffold for ARP.
Understanding effective post‐test linkage strategies for HIV prevention and care: a scoping review
Authors: Wamuti Beatrice , Jamil Muhammad S. , Siegfried Nandi , Ford Nathan , Baggaley Rachel , Johnson Cheryl Case , Cherutich Peter 
Published: April 2024

AbstractIntroductionFollowing HIV testing services (HTS), the World Health Organization recommends prompt linkage to prevention and treatment. Scale‐up of effective linkage strategies is essential to achieving the global 95‐95‐95 goals for maintaining low HIV incidence by 2030 and reducing HIV‐related morbidity and mortality. Whereas linkage to care including same‐day antiretroviral therapy (ART) initiation for all people with HIV is now routinely implemented in testing programmes, linkage to HIV prevention interventions including behavioural or biomedical strategies, for HIV‐negative individuals remains sub‐optimal. This review aims to evaluate effective post‐HTS linkage strategies for HIV overall, and highlight gaps specifically in linkage to prevention.MethodsUsing the five‐step Arksey and O'Malley framework, we conducted a scoping review searching existing published and grey literature. We searched PubMed, Cochrane Library, CINAHL, Web of Science and EMBASE databases for English‐language studies published between 1 January 2010 and 30 November 2023. Linkage interventions included as streamlined interventions—involving same‐day HIV testing, ART initiation and point‐of‐care CD4 cell count/viral load, case management—involving linkage coordinators developing personalized HIV care and risk reduction plans, incentives—financial and non‐financial, partner services—including contact tracing, virtual—like social media, quality improvement—like use of score cards, and peer‐based interventions. Outcomes of interest were linkage to any form of HIV prevention and/or care including ART initiation.ResultsOf 2358 articles screened, 66 research studies met the inclusion criteria. Only nine linkage to prevention studies were identified (n = 9/66, 14%)—involving pre‐exposure prophylaxis, voluntary medical male circumcision, sexually transmitted infection and cervical cancer screening. Linkage to care studies (n = 57/66, 86%) focused on streamlined interventions in the general population and on case management among key populations.DiscussionDespite a wide range of HIV prevention interventions available, there was a dearth of literature on HIV prevention programmes and on the use of messaging on treatment as prevention strategy. Linkage to care studies were comparatively numerous except those evaluating virtual interventions, incentives and quality improvement.ConclusionsThe findings give insights into linkage strategies but more understanding of how to provide these effectively for maximum prevention impact is needed.
Moisture sources of precipitation over the Pearl River Basin in South China
Authors: Liu Xinxin , Guo Chengchao , Zhang Jingkun , Liu Yang , Xiao Mingzhong , Wu Yongyan , Li Bo , Zhao Tongtiegang 
Published: April 2024

AbstractMoisture sources and transport processes play a critical part in hydrological cycle and determine regional precipitation. This paper utilizes the Water Accounting Model‐2layers (WAM‐2layers) and the ERA5 reanalysis data to track the sources of precipitation over the Pearl River Basin (PRB). The contribution of external moisture and the role of local recycling are investigated. The results show that during the period from 1980 to 2020, oceanic sources including the western North Pacific and Indian Oceans serve as the primary moisture sources of precipitation over the PRB. The contributions to total seasonal precipitation are respectively 62.57% in MAM, 54.79% in JJA, 43.70% in SON and 60.88% in DJF. By contrast, the contribution of local recycling is generally below 5.50%. In the dry years of 1994, 1997 and 2001, the contribution of terrestrial sources is about 19.22%; in the wet years of 1989, 2009 and 2011, the contribution is about 16.31%. The summer precipitation anomalies are mainly attributable to moisture anomalies from the Equatorial Indian Ocean in the wet years and from Southeast Asia in the dry years. Furthermore, vertically integrated moisture flux anomalies over the boundaries of the PRB are generally the result of anomalous wind rather than anomalous moisture. In the wet years, low‐pressure systems induce strong cyclonic moisture transports, increasing the PRB precipitation. In the dry years, high‐pressure anomalies over the PRB block the moisture transports from the Indian Ocean and western North Pacific.
Evaluating the performance of key ERA‐Interim, ERA5 and ERA5‐Land climate variables across Siberia
Authors: Clelland Andrew A. , Marshall Gareth J. , Baxter Robert 
Published: April 2024

AbstractReanalysis datasets provide a continuous picture of the past climate for every point on Earth. They are especially useful in areas with few direct observations, such as Siberia. However, to ensure these datasets are sufficiently accurate they need to be validated against readings from meteorological stations. Here, we analyse how values of six climate variables—the minimum, mean and maximum 2‐metre air temperature, snow depth (SD), total precipitation and wind speed (WSP)—from three reanalysis datasets—ERA‐Interim, ERA5 and ERA5‐Land—compare against observations from 29 meteorological stations across Siberia and the Russian Far East on a daily timescale from 1979 to 2019. All three reanalyses produce values of the mean and maximum daily 2‐metre air temperature that are close to those observed, with the average absolute bias not exceeding 1.54°C. However, care should be taken for the minimum 2‐metre air temperature during the summer months—there are nine stations where correlation values are <0.60 due to inadequate night‐time cooling. The reanalysis values of SD are generally close to those observed after 1992, especially ERA5, when data from some of the meteorological stations began to be assimilated, but the reanalysis SD should be used with caution (if at all) before 1992 as the lack of assimilation leads to large overestimations. For low daily precipitation values the reanalyses provide good approximations, however they struggle to attain the extreme high values. Similarly, for the 10‐metre WSP; the reanalyses perform well with speeds up to 2.5 ms−1 but struggle with those above 5.0 ms−1. For these variables, we recommend using ERA5 over ERA‐Interim and ERA5‐Land in future research. ERA5 shows minor improvements over ERA‐Interim, and, despite an increased spatial resolution, there is no advantage to using ERA5‐Land.