bluuebunny/crossref_metadata_2025_split huggingface dataset:
Insights into the Interfacial Charge Transfer Dynamics in Semiconductor–Molecular Catalyst Assemblies for Photo–Induced CO2 Reduction
Authors: Chatterjee Tamal , Domingo‐Tafalla Beatriu , Ballester Pablo , Palomares Emilio 
Published: June 2024

AbstractThis mini–review summarises examples of photo and photoelectrochemical CO2 reduction reactions (CO2RR) using semiconductor–molecular catalyst–based hybrid assemblies in which studies of charge transfer dynamics were also performed. In these catalysts, the grand challenges are controlling ultra–fast one–electron charge separation and simultaneously governing its impact on the efficiency and product selectivity in the multielectron and multi–proton–assisted CO2RR. In practice, several unwanted electron recombination processes occur in the femtosecond to millisecond timescale range impacting the overall catalysis efficiency. Titanium di‐oxide (TiO2) nanoparticle, mesoporous TiO2 film, copper indium sulphide (CuInS2) quantum dots were used as semiconductor materials, in turn rhenium (I) bipyridine, cobalt (II) terpyridine, cobaloxamine complex, and iron (III) porphyrins were investigated as molecular catalysts. The results of the charge transfer dynamic studies operating in such hybrid systems shed light on their charge accumulation processes, their rate constants for the intramolecular charge transfer processes and the decay lifetimes of the different excited state species that are produced. Moreover, a comprehensive understanding of the catalysts’ charge transfer dynamics is crucial to identifying detrimental charge recombination pathways. These undesired pathways can be used as rational basis for improving the design of future multi–redox–driven hybrid catalysts.
Copper‐Catalyzed Tunable Oxygenative Rearrangement of Tetrahydrocarbazoles
Authors: Ren Hai , Yang Bing‐Qing , Shi Jun , Wu Wei , Jiang Biaobiao , Chi Qin 
Published: June 2024

AbstractHerein, we report a general copper‐catalyzed method for the tunable oxygenative rearrangement of tetrahydrocarbazoles to cyclopentyl‐bearing spiroindolin‐2‐ones and spiroindolin‐3‐ones. The method demonstrates excellent chemoselectivity, regioselectivity, and product control simply by using the H2O and O2 as oxygen source, respectively. This open‐flask method is safe and simple to operate, and no other chemical oxidants are required. Besides, inspired from the unique pathway of 1, 2‐migration rearrangement, a highly controllable hydroxylation of indoles for the construction of C3a‐hydroxyl iminium indolines was also developed. Mechanistic experiments suggest that a single‐electron transfer‐induced oxidation process is responsible for the tunable selectivity control.
Diastereo‐ and Enantioselective Construction of Stereochemical Arrays Exploiting Non‐Classical Hydrogen Bonding in Enolborates
Authors: Li Matthew , Scheeff Stephan , Chen Jiahua , Johnston Ryne C. , Rizzo Antonio , Krenske Elizabeth H. , Chiu Pauline 
Published: June 2024

AbstractWe report a copper‐catalyzed reductive aldol addition to aldehydes and ketones, with pinacolborane as stoichiometric reductant, that results in the generation of stereodefined syn‐aldol products. Cyclic, acyclic, fused and spirocyclic aldols bearing contiguous stereocenters are obtained with excellent yields and diastereoselectivities. Moreover, enantioselective reactions could be carried out with cycloalkenones to deliver aldols bearing three contiguous stereocenters and with up to 98 % ee. Computations reveal that the enolborate intermediate undergoes the syn‐aldol reaction via a twist‐boat transition state that is stabilized by non‐classical hydrogen bonding interactions.
Photoredox Catalysis by 21‐Thiaporphyrins: A Green and Efficient Approach for C−N Borylation and C−H Arylation
Authors: Janaagal Anu , Kushwaha Apoorv , Jhaldiyal Pranjali , Dhilip Kumar T. J. , Gupta Iti 
Published: June 2024

AbstractPhotoredox catalysis provides a green and sustainable alternative for C−H activation of organic molecules that eludes harsh conditions and use of transition metals. The photocatalytic C−N borylation and C−H arylation mostly depend on the ruthenium and iridium complexes or eosin Y and the use of porphyrin catalysts is still in infancy. A series of novel 21‐thiaporphyrins (A2B2 and A3B type) were synthesized having carbazole/phenothiazine moieties at their meso‐positions and screened as catalysts for C−N borylation and C−H arylation. This paper demonstrates the 21‐thiaporphyrin catalyzed C−N borylation and het‐arylation of anilines under visible light. The method utilizes only 0.1 mol % of 21‐thiaporphyrin catalyst under blue light for the direct C−N borylation and het‐arylation reactions. A variety of substituted anilines were used as source for expensive and unstable aryl diazonium salts in the reactions. The heterobiaryls and aryl boronic esters were obtained in decent yields (up to 88 %). Versatility of the 21‐thiaporphyrin catalyst was tested by thiolation and selenylation of anilines under similar conditions. Mechanistic insight was obtained from DFT studies, suggesting that 21‐thiaporphyrin undergo an oxidative quenching pathway. The photoredox process catalyzed by 21‐thiaporphyrins offers a mild, efficient and metal‐free alternative for the formation of C−C, C−S, and C−Se bonds in aryl compounds; it can also be extended to borylation reaction.
Color Polymorphism and Room Temperature Phosphorescence of 4‐Bromo‐2,7‐Di‐Tert‐Butyl‐ 9‐Methoxypyrene
Authors: Morawski Olaf W. , Karpiuk Jerzy , Grzybowski Marek 
Published: June 2024

AbstractColor polymorphism combined with crystal packing‐dependent luminescence properties of polymorphs reflects differences in intermolecular interactions in different molecular arrangements. The title compound has two polymorphic crystal structures having strikingly different absorption and luminescence spectra that result from different packing motifs in the crystal lattice. The polymorph with brick wall‐like packing of molecules is white and shows very weak violet fluorescence whereas the second polymorph, where molecules are arranged in columnar stacks, is bright yellow and displays intense green fluorescence with maximum at 487 nm (20530 cm−1). In the white polymorph, where the distance between neighboring chromophores is increased, absorption and fluorescence spectra are similar to those of monomer in solution, and intersystem crossing to triplet manifold is the dominant pathway of relaxation. In the yellow polymorph, molecules within the columnar stacks are rotated which mitigates the steric hindrance and leads to closer π‐stacking of the pyrene cores. That increases the ππ overlap and strengthens intermolecular interactions decreasing energy of the excited states. This affects emission spectra and photophysical processes–fluorescence yield grows whereas triplet formation yield decreases when S1 is lowered below higher triplet states and conditions for effective vibronic spin‐orbit coupling are not favorable. The effect is not observed for other similar pyrene derivatives, testifying the uniqueness of the phenomenon.
Comparing two recurrent selection methods for developing superior apomictic hybrids in Paspalum notatum
Authors: Marcón Florencia , Galanter Iru N. Lezcano , Brugnoli Elsa A. , Zilli Alex L. , Martínez Eric J. , Acuña Carlos A. 
Published: June 2024

AbstractRecurrent selection methods have been successful in generating superior Paspalum notatum families through the accumulation of favorable alleles. However, the effectiveness of these methods in producing apomictic hybrids with superior agronomic traits has not been thoroughly evaluated. The aim of this study was to characterize the reproductive behavior of P. notatum progenies obtained through recurrent selection based on combining ability (RSCA) and recurrent phenotypic selection (RPS) and assess the performance of the apomictic hybrids concerning various agronomic traits. The reproductive mode of 144 RSCA and 144 RPS hybrids was determined using a molecular marker tightly linked to the apospory trait (BCU243‐377). The expressivity of apospory was estimated observing mature embryo sacs. The apomictic hybrids were then evaluated for six agronomic traits. A segregation ratio of 5:1 between sexual and apomictic hybrids was observed for the RSCA progeny, while 4.3:1 was registered for the RPS progeny. Although apospory expressivity was variable among hybrids, 75% and 86% of the RSCA and RPS hybrids, respectively, exhibited a high expression (>81%). Non‐significant differences between breeding methods in the number of apomictic hybrids and the level of apospory expressivity were observed. Variations for all agronomic traits were observed among apomictic hybrids within each breeding method. However, no differences between methods in the performance of the highly apomictic hybrids were observed. This demonstrates that the reproductive behavior of P. notatum is not affected by the recurrent selection method. Therefore, the RPS method would be the most suitable since it was equally effective than RSCA but it is cheaper, faster, and easier to apply.
Sulfonate Group Improves the Solubility and Electrocatalytic Performance of Ru‐Based bda‐ and pda‐Type Water Oxidation Catalysts under Neutral Conditions
Authors: Kerkhof Jake T. , Breyer Colton J. , Smith Diane K. , Mao Yuezhi , Grotjahn Douglas B. 
Published: June 2024

AbstractFour ruthenium water oxidation catalysts that bear carboxylate and sulfonate groups in the active site have been synthesized and analyzed for their catalytic activity. The sulfonate‐containing catalysts show higher electrochemical activity in pH 7 phosphate buffer with 4 times larger catalytic current, improved durability with sacrificial oxidant, and increased solubility compared to similar species containing two carboxylate groups. Density functional theory calculations suggest that the sulfonate group provides a more favorable geometry for water nucleophilic attack, which is both the energetically most favorable mechanism calculated and the experimentally predicted mechanism under electrochemical conditions. Further experimental studies have been performed to show that under certain conditions catalysts can perform well electrochemically under pH conditions as low as 1.6 and that various structural components can greatly change solubility and catalytic operation.
Alpha‐Gal Syndrome: An Underrated Serious Disease and a Potential Future Challenge
Authors: Zhan Mengyuan , Yin Jia , Xu Tengda , Wen Liping 
Published: June 2024

AbstractOver the past decades, red meat allergy, also known as mammalian meat allergy, which manifests differently from classic food allergies, has been reported in different countries and regions, including China. The allergen of this disease is not a protein but an oligosaccharide: galactose‐α‐1,3‐galactose, i.e., alpha‐gal or α‐gal. Therefore, this clinical syndrome is also called α‐gal syndrome (AGS). It clinically manifests as delayed anaphylaxis, i.e., patients generally develop allergic symptoms 2–6 h after ingesting red meat. This clinical manifestation is believed to be related to sensitization to α‐gal after tick bites. Sensitized individuals may also develop anaphylaxis after ingesting food and medicine or being exposed to medical equipment containing α‐gal, such as cetuximab and gelatin. Here, the literature on AGS is reviewed for a better understanding of its pathogenesis, clinical diagnosis, and treatment.
The effects of spatial leakage correction on the reliability ofEEG‐based functional connectivity networks
Authors: Nagy Péter , Tóth Brigitta , Winkler István , Boncz Ádám 
Published: June 2024

AbstractElectroencephalography (EEG) functional connectivity (FC) estimates are confounded by the volume conduction problem. This effect can be greatly reduced by applying FC measures insensitive to instantaneous, zero‐lag dependencies (corrected measures). However, numerous studies showed that FC measures sensitive to volume conduction (uncorrected measures) exhibit higher reliability and higher subject‐level identifiability. We tested how source reconstruction contributed to the reliability difference of EEG FC measures on a large (n = 201) resting‐state data set testing eight FC measures (including corrected and uncorrected measures). We showed that the high reliability of uncorrected FC measures in resting state partly stems from source reconstruction: idiosyncratic noise patterns define a baseline resting‐state functional network that explains a significant portion of the reliability of uncorrected FC measures. This effect remained valid for template head model‐based, as well as individual head model‐based source reconstruction. Based on our findings we made suggestions how to best use spatial leakage corrected and uncorrected FC measures depending on the main goals of the study.
Response of runoff and its components to climate change and its future trend in the source region of the Yangtze River
Authors: Gao Tailai , Li Jiadi , Tang Yuanzhi , Jiang Xiaoxuan , Huo Junjun 
Published: June 2024

AbstractUnder global climate changes, the temperature and precipitation on the Tibetan Plateau changed significantly, causing accelerated melting of glaciers and snow and changes in runoff. The response of runoff and its components to climate change is important for water resource management and ecology conservation in the region. Therefore, the Spatial Processes in Hydrology model, a distributed cold‐zone hydrological model that contains a glacial ablation module, was used to simulate runoff in the Yangtze River source located in the middle of the Tibetan Plateau during 2000–2050, and the Nash‐Sutcliffe efficiency coefficient, relative error and coefficient of determination (R2) for the calibration period and validation period revealed that the model performed well in most years. The results showed that rainfall runoff contributed the most to the total runoff (61%), followed by baseflow (23%), snowmelt runoff (12%) and glacier runoff (4%) in the Yangtze River source during 2000–2020. The runoff amounts of the three source rivers, Dangqu River, Tuotuo River and Chumar River, accounted for approximately 53% of the total runoff in the Yangtze River source basin, with rainfall runoff (52%) contributing the most and glacier runoff (6%) contributing the least. Compared to the contributions of glacial runoff in the Dangqu River (9%) and Tuotuo River (7%), the proportion of glacial runoff in the Chumar River is small (1%). Under the CMIP6 climate model, the mean runoff depth is predicted to increase by approximately 13.5 mm from 2020 to 2050 compared with that from 2000 to 2020.
Idealized branch sections and hydrodynamic analysis characterize rainfall partitioning
Authors: Puri Aryan , Kunadi Ashvath , Pfefferle David , Ghisalberti Marco , Thompson Sally 
Published: June 2024

AbstractWater flow on plant canopies determines the partitioning of intercepted rainfall between stemflow and throughflow, yet understanding of these flow processes remains minimally developed. Plant canopies may concentrate intercepted water into rivulets that flow beneath branches. If the rivulets remain attached to branches until they encounter the main tree trunk, they form stemflow. If the rivulets detach from branches, however, they form ‘pour points’, regions of concentrated throughfall. Here, rivulet flow below uniform cylinders was studied experimentally. Experimental observations were interpreted using hydrodynamic theory to predict the likelihood of a rivulet detaching based on a critical rivulet height (). Predictions of rivulet detachment were explored for a simplified case where water is introduced at known flow rates at a discrete point above a uniform, cylindrical ‘branch’. Where the branch was straight, the percentage of trials forming a rivulet, or the rivulet formation rate, increased with increasing branch inclination angle to the horizontal axis. Rivulet formation rates did not vary with flow rate. However, the volume of water collected at the end of the branch, analogous to stemflow, decreased with a higher flow rates due to the formation of flow instabilities. Rivulets forming on straight branches did not detach. Instead, the rivulet stream accelerated and reduced in height as it flowed along the cylinder. Rivulets formed on curved branches detached only when the branch axis after the curve approached the horizontal. Future theoretical and experimental studies can extend this work to improve understanding of more complex surfaces and branch architectures to mechanistically understand canopy interception.
Three‐dimensional bioprinting biphasic multicellular living scaffold facilitates osteochondral defect regeneration
Authors: Yu Xingge , Gholipourmalekabadi Mazaher , Wang Xudong , Yuan Changyong , Lin Kaili 
Published: June 2024

AbstractDue to tissue lineage variances and the anisotropic physiological characteristics, regenerating complex osteochondral tissues (cartilage and subchondral bone) remains a great challenge, which is primarily due to the distinct requirements for cartilage and subchondral bone regeneration. For cartilage regeneration, a significant amount of newly generated chondrocytes is required while maintaining their phenotype. Conversely, bone regeneration necessitates inducing stem cells to differentiate into osteoblasts. Additionally, the construction of the osteochondral interface is crucial. In this study, we fabricated a biphasic multicellular bioprinted scaffold mimicking natural osteochondral tissue employing three‐dimensional (3D) bioprinting technology. Briefly, gelatin‐methacryloyl (GelMA) loaded with articular chondrocytes and bone marrow mesenchymal stem cells (ACs/BMSCs), serving as the cartilage layer, preserved the phenotype of ACs and promoted the differentiation of BMSCs into chondrocytes through the interaction between ACs and BMSCs, thereby facilitating cartilage regeneration. GelMA/strontium‐substituted xonotlite (Sr‐CSH) loaded with BMSCs, serving as the subchondral bone layer, regulated the differentiation of BMSCs into osteoblasts and enhanced the secretion of cartilage matrix by ACs in the cartilage layer through the slow release of bioactive ions from Sr‐CSH. Additionally, GelMA, serving as the matrix material, contributed to the reconstruction of the osteochondral interface. Ultimately, this biphasic multicellular bioprinted scaffold demonstrated satisfactory simultaneous regeneration of osteochondral defects. In this study, a promising strategy for the application of 3D bioprinting technology in complex tissue regeneration was proposed.
Spatially and Single‐Cell Resolved Profiling of RNA Life Cycle and Epitranscriptomics
Authors: Zhou Qiyang , Guo Jianting , Wang Xiao 
Published: June 2024

AbstractThe intricate network of cell functions relies on gene expression programs, where the whole RNA life cycle from DNA to protein is subjected to extensive transcriptional and post‐transcriptional gene regulation events. Established bulk RNA sequencing methods provide an averaged, transcriptome‐wide quantification of the RNA life cycle, including transcription, processing, translation, transport, and degradation through RNA‐protein interactions. Furthermore, numerous studies using bulk epitranscriptomic profiling unveiled that dynamic RNA modifications (e. g., N6‐Methyladenosine), add another layer of gene regulations. However, many regulatory events are cell‐type specific, subcellularly localized, and subjected to cell‐cell communications within the native tissue environment. Thanks to the advances in single‐cell sequencing, spatial sequencing, and highly multiplexed imaging methods, we can routinely measure single‐cell and spatial transcriptomics. Yet more comprehensive methods to profile every step of the RNA life cycle with single‐cell and spatial information are still lacking. In this review, we will summarize and compare early explorations in developing state‐of‐the‐art methods for spatially and single‐cell resolved mapping of RNA kinetics, translation, RNA‐protein interactions, and epitranscriptomics. It is promising that these new techniques will greatly facilitate our understanding of the RNA‐centered regulation landscapes in different cell types and how the post‐transcriptional regulations are interconnected within cellular and tissue architecture.
LncRNA MEG3 regulates ferroptosis of lens epithelial cells via PTBP1/GPX4 axis to participate in age‐related cataract
Authors: Zhang Xinyuan , Zheng Chuanfei , Zhao Jiuhong , Xu Xiaoming , Yao Jun 
Published: June 2024

AbstractAge‐related cataract (ARC) is regarded as the principal cause of vision impairment among the aged. The regulatory role of long noncoding RNAs (LncRNAs) in ARC remains unclear. The lncRNA maternally expressed gene 3 (MEG3) has been reported to promote ARC progression, and the underlying mechanism was further investigated in this study. Lens epithelium samples were collected to verify the expression of MEG3. Lens epithelial cells (LECs) were treated with H2O2 to mimic microenvironment of ARC in vitro. Cell viability, reactive oxygen species, and ferroptosis were evaluated during the in viro experiments. In the present work, lncRNA MEG3 was highly expressed in ARC group, compared with normal group. MEG3 was induced, cell viability and glutathione peroxidase 4 (GPX4) level were inhibited, and ferroptosis was promoted in H2O2 treated LECs. LncRNA MEG3 silence reversed the effects of H2O2 on viability and ferroptosis in LECs. Thereafter, lncRNA MEG3 was found to bind to PTBP1 for GPX4 degradation. Silencing of GPX4 reversed the regulation of lncRNA MEG3 inhibition in H2O2‐treated LECs. To sum up, lncRNA MEG3 exhibited high expression in ARC. In H2O2‐induced LECs, inhibition of lncRNA MEG3 accelerated cell viability and repressed ferroptosis by interaction with PTBP1 for GPX4 messenger RNA decay. Targeting lncRNA MEG3 may be a novel treatment of ARC.
Counting connected partitions of graphs
Authors: Caro Yair , Patkós Balázs , Tuza Zsolt , Vizer Máté 
Published: June 2024

AbstractMotivated by the theorem of Győri and Lovász, we consider the following problem. For a connected graph on vertices and edges determine the number of unordered solutions of positive integers such that every is realized by a connected subgraph of with edges. We also consider the vertex‐partition analogue. We prove various lower bounds on as a function of the number of vertices in , as a function of the average degree of , and also as the size of ‐partite connected maximum cuts of . Those three lower bounds are tight up to a multiplicative constant. We also prove that the number of unordered ‐tuples with , that are realizable by vertex partitions into connected parts, is at least .
心尖部心室瘤を有する心室中部閉塞性肥大型心筋症に合併したKounis症候群の1例(A case of Kounis syndrome with midventricular obstructive hypertrophic cardiomyopathy with apical aneurysm)
Authors: 朋子 菅野 , 高寛 湯川 , 里織 大坪 , 武志 山際 
Published: June 2024

要旨Kounis症候群とはアレルギー反応に伴い急性冠症候群を来す疾患である。今回我々は，肥大型心筋症にKounis症候群を合併した症例を経験したため報告する。症例は45歳の女性。抗菌薬を初回内服後，皮膚の掻痒感と呼吸困難感を自覚し救急搬送された。来院時橈骨動脈の触知微弱であり，全身皮膚紅潮と膨疹を認め，アナフィラキシーショックと診断しアドレナリン0.3mgを計2回大腿外側に筋肉注射した。また，心電図でII，III，aVF，V1–V5のSTおよび心筋逸脱酵素の上昇，心エコーで心尖部心室瘤を認めた。来院後30分間程度ショックが遷延したが，次第に安定した。急性冠症候群を疑い緊急冠動脈造影検査を施行したが両側冠動脈に有意狭窄は認めず，Kounis症候群タイプIと診断した。また，心臓造影MRI検査で左心室中部の心筋壁が肥厚しており，心尖部心室瘤を有する心室中部閉塞性肥大型心筋症と診断し，肥大型心筋症へのアドレナリン投与がショックの遷延に影響したと考えられた。アナフィラキシーショックの初期治療後もショックが遷延した場合は迅速に心電図，心エコーを実施し，Kounis症候群や既存心疾患の病態増悪を鑑別に挙げる必要がある。また，Kounis症候群に心室中部閉塞性肥大型心筋症などの心疾患を合併した場合は，薬物治療の選択に注意が必要である。