bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mimicking Ozonolysis via Mechanochemistry: Internal Alkynes to 1,2‐Diketones using H5IO6
Authors: Nayek Pravat , Mal Prasenjit 
Published: April 2024

AbstractUtilizing periodic acid as an environmentally benign oxidizing agent, this study introduces a novel mechanochemical method that mimics ozonolysis to convert internal alkynes into 1,2‐diketones, showcasing effective emulation of ozone‘s reactivity. Notably, this oxidation occurs at room temperature in aerobic conditions, eliminating the need for toxic transition metals, hazardous oxidants, or expensive solvents. Through control experiments validating the mechanism, substantial evidence supports a concerted reaction pathway. This progress marks a significant stride toward cleaner and more efficient chemical synthesis, mitigating the environmental impact of conventional processes. Assessing the green chemistry metrics in both solvent‐free and previously reported solvent‐based methods, our eco‐friendly protocol demonstrates an E‐factor of 7.40, a 51.7 % atom economy, a 45.5 % atom efficiency, 100 % carbon efficiency, and 11.9 % reaction mass efficiency when solvents are not used.
Surface Functionalized Titanium Nitride Electrode for CMOS Compatible Bioelectronic Devices
Authors: Yu Meng , Tang Xiaohui , Yang Shijia , Li Zhenhua , Chen Chang , Xie Sijia 
Published: April 2024

AbstractThe development of bioelectronic devices is heading toward high throughput and high resolution. Yet, most electrode materials utilized in electrical biosensing are not compatible with the manufacturing techniques of semiconductor chips, which somehow hinders the integration and miniaturization of these devices. Titanium nitride (TiN) is a durable and economical material that is widely used in CMOS‐based integrated circuits, bioelectronic systems, electrocatalytic systems, etc. Considering different application scenarios, new and efficient methods are required to functionalize TiN surface. In this study, a surface functionalization approach by covalent grafting of an organic thin film containing hydroxyl groups on TiN surface via electroreduction of diazonium salt 4‐(2‐hydroxyethyl)benzenediazonium was presented. Cyclic voltammetry (CV) procedures were carried out at the potential ranges of −0.8 V~0.5 V (vs Ag/AgCl) with varying numbers of potential cycles (i. e., 5, 25, and 50 cycles) in order to study the thickness of modification layer. Then, the electrochemical property, surface morphology, and chemical structures of the sample before and after modifications were investigated via multiple characterization techniques, such as CV, atomic force microscopy (AFM), scanning electron microscope (SEM) and X‐ray photoelectron spectroscopy (XPS), etc., thereby confirming the successful grafting of hydroxyl groups onto the TiN surface. The experiments on DNA synthesis aimed to explore the potential of modified TiN electrode as a novel platform for DNA data storage applications and the corresponding proof‐of‐principle was accomplished by the process of coupling Cy3‐phosphoramidite. Finally, the experiments were successfully reproduced on the randomly selected sites of the modified TiN microarray chips demonstrating the potential of technical protocol to extend applications in future bioelectronic devices, such as bio‐sensing, high‐throughput DNA synthesis, and molecular manipulation.
Folding of the cerebellar cortex is clade‐specific in form but universal in degree
Authors: York Annaleigh R. , Sherwood Chet C. , Manger Paul R. , Kaas Jon H. , Mota Bruno , Herculano‐Houzel Suzana 
Published: April 2024

AbstractLike the cerebralcortex, the surface of the cerebellum is repeatedly folded. Unlike the cerebralcortex, however, cerebellar folds are much thinner and more numerous; repeatthemselves largely along a single direction, forming accordion‐like folds transverseto the mid‐sagittal plane; and occur in all but the smallest cerebella. We haveshown previously that while the location of folds in mammalian cerebral cortex isclade‐specific, the overall degree of folding strictly follows a universalpower law relating cortical thickness and the exposed and total surface areas predictedfrom the minimization of the effective free energy of an expanding, self‐avoidingsurface of a certain thickness. Here we show that this scaling law extends tothe folding of the mid‐sagittal sections of the cerebellum of 53 speciesbelonging to six mammalian clades. Simultaneously, we show that each clade hasa previously unsuspected distinctive spatial pattern of folding evident at themid‐sagittal surface of the cerebellum. We note, however, that the mammaliancerebellum folds as a multi‐fractal object, because of the difference betweenthe outside‐in development of the cerebellar cortex around a preexisting coreof already connected white matter, compared to the inside‐out development ofthe cerebral cortex with a white matter volume that develops as the cerebralcortex itself gains neurons. We conclude that repeated folding, one of the mostrecognizable features of biology, can arise simply from the interplay betweenthe universal applicability of the physics of self‐organization and biological,phylogenetical clade‐specific contingency, without the need for invokingselective pressures in evolution.
Decarboxylative Ketonization of Aliphatic Carboxylic Acids in a Continuous Flow Reactor Catalysed by Manganese Oxide on Silica
Authors: Goebel Jonas F. , Belitz Florian , Prendes Daniel Sowa , Haver Yannik , Diehl Patrick , Muhler Martin , Gooßen Lukas J. 
Published: April 2024

AbstractThe sustainable synthesis of long carbon chain molecules from carbon dioxide, water and electricity relies on the development of waste‐free, highly selective C−C bond forming reactions. An example for such a power‐to‐chemicals process is the industrial‐scale fermentation for the production of hexanoic acid. Herein, we describe how this product is transformed into 6‐undecanone via decarboxylative ketonization using a heterogeneous manganese oxide/silica catalyst. The reaction reaches full conversion with near‐complete selectivity when carried out in a continuous flow reactor, requires no solvent or carrier gas, and releases carbon dioxide and water as the only by‐products. The reactor was operated for several weeks with no loss of reactivity, producing 7 kg of 6‐undecanone from 10 g of catalyst and achieving a productivity of 1.135 kg per litre of reactor volume per hour. 6‐Undecanone and other long‐chain ketones accessible this way can be hydrogenated to industrially meaningful alkanes, or converted into valuable fatty acids via a hydrogenation/elimination/isomerizing hydrocarboxylation sequence.
OMIP‐102: 50‐color phenotyping of the human immune system with in‐depth assessment of T cells and dendritic cells
Authors: Konecny Andrew J. , Mage Peter L. , Tyznik Aaron J. , Prlic Martin , Mair Florian 
Published: April 2024

AbstractWe report the development of an optimized 50‐color spectral flow cytometry panel designed for the in‐depth analysis of the immune system in human blood and tissues, with the goal of maximizing the amount of information that can be collected using currently available flow cytometry platforms. We established and tested this panel using peripheral blood mononuclear cells (PBMCs), but included CD45 to enable its future use for the analysis of human tissue samples. The panel contains lineage markers for all major immune cell subsets, and an extensive set of phenotyping markers focused on the activation and differentiation status of the T cell and dendritic cell (DC) compartment. We outline the biological insight that can be gained from the simultaneous measurement of such a large number of proteins and propose that this approach provides a unique opportunity for the comprehensive exploration of the immune status in human samples with a limited number of cells. Of note, we tested the panel to be compatible with cell sorting for further downstream applications. Furthermore, to facilitate the wide‐spread implementation of such a panel across different cohorts and samples, we established a trimmed‐down 45‐color version which can be used with different spectral cytometry platforms. Finally, to generate this panel, we utilized not only existing panel design guidelines, but also developed new metrics to systematically identify the optimal combination of 50 fluorochromes and evaluate fluorochrome‐specific resolution in the context of a 50‐color unmixing matrix.
In vitro and in silico investigation of FDA‐approved drugs to be repurposed against Alzheimer's disease
Authors: Akkaya Didem , Seyhan Gökçe , Sari Suat , Barut Burak 
Published: April 2024

AbstractAlzheimer's disease (AD), one of the main causes of dementia, is a neurodegenerative disorder. Cholinesterase inhibitors are used in the treatment of AD, but prolonged use of these drugs can lead to serious side effects. Drug repurposing is an approach that aims to reveal the effectiveness of drugs in different diseases beyond their clinical uses. In this work, we investigated in vitro and in silico inhibitory effects of 11 different drugs on cholinesterases. The results showed that trimebutine, theophylline, and levamisole had the highest acetylcholinesterase inhibitory actions among the tested drugs, and these drugs inhibited by 68.70 ± 0.46, 53.25 ± 3.40, and 44.03 ± 1.20%, respectively at 1000 µM. In addition, these drugs are bound to acetylcholinesterase via competitive manner. Molecular modeling predicted good fitness in acetylcholinesterase active site for these drugs and possible central nervous system action for trimebutine. All of these results demonstrated that trimebutine was determined to be the drug with the highest potential for use in AD.
Size matters: Natural experiments suggest the dear enemy effect is moderated by pack size in African wild dogs
Authors: Claase Megan J. , Cherry Mike I. , McNutt J. Weldon , Apps Peter J. , Jordan Neil R. 
Published: April 2024

AbstractRemote monitoring of communal marking sites, or latrines, provides a unique opportunity to observe undisturbed scent marking behaviour of African wild dogs (Lycaon pictus). We used remote camera trap observations in a natural experiment to test behavioural scent mark responses to rivals (either familiar neighbours or unfamiliar strangers), to determine whether wild dogs exhibit the “dear enemy” or “nasty neighbour” response. Given that larger groups of wild dogs represent a greater threat to smaller groups, including for established residents, we predicted that the overarching categories “dear enemy” vs. “nasty neighbour” may be confounded by varying social statuses that exists between individual dyads interacting. Using the number of overmarks as a metric, results revealed an interaction between sender and receiver group size irrespective of familiarity consistent with this prediction: in general, individuals from large resident packs overmarked large groups more than they overmarked smaller groups, whereas individuals from smaller packs avoided overmarking larger groups, possibly to avoid detection. Monitoring a natural system highlights variables such as pack size that may be either overlooked or controlled during scent presentation experiments, influencing our ability to gain insights into the factors determining territorial responses to rivals.
Quantifying the roles of climate, herbivory, topography, and vegetation on tree establishment in the treeline ecotone
Authors: Mienna Ida M. , Klanderud Kari , Næsset Erik , Gobakken Terje , Bollandsås Ole Martin 
Published: April 2024

AbstractThe transition zone between the upper forest boundary and the treeless alpine vegetation (i.e., the treeline ecotone) is expected to shift upward in elevation with global warming. Multiple factors in addition to climate are influencing tree establishment, but it is uncertain to what degree. In this study, we took advantage of a unique dataset with field measurements of mountain birch trees acquired from 32 boreal–alpine treeline ecotone sites situated along a 1100‐km latitudinal gradient in Norway to investigate the role of climate, herbivory, topography, and vegetation on the establishment success of trees. To represent tree establishment, we recorded occurrence, survival, and height growth of short juvenile birch trees (stem height ≤1 m) as response variables at each site in 2008, 2012, and 2018. We used already available climate and herbivory data, and airborne laser scanning (ALS) and unmanned aerial vehicle (UAV) surveyed imagery together with field measurements to compute topography and vegetation explanatory variables per site on microsite scale (approx. 1 m2). We observed a clear decrease in short juvenile birch tree establishment due to livestock herbivory, evidenced by lower occurrence, reduced survival rate, and diminished height growth in treeline ecotones with higher livestock densities. Winter precipitation and the two land cover classes, tree‐covered area and lee side vegetation, were also important for tree establishment. However, the direction and magnitude of the relationships depended on the stage of establishment. While winter precipitation can lead to higher tree occurrence, long‐term survival is not necessarily ensured, reflecting diverse requirements for optimal conditions of tree establishment. Thus, our results show that occurrence, survival, and height growth of short juvenile birch trees differ in their requirements to climate, topography, and vegetation, but tree establishment is consistently low with livestock herbivory. Overall, our results suggest that treeline ecotones will shift toward higher elevations in areas with little or no livestock herbivory and close to already established trees and in lee sides. Regarding management and conservation issues, our results suggest that free‐roaming livestock can reduce tree establishment and hinder treeline ecotone shifts into threatened alpine ecosystems, at least for birch‐dominated treelines.
Tiny niche terrain induces gully headcut retreat
Authors: Wang Chao , Cai Chongfa , Deng Yusong 
Published: April 2024

AbstractGully erosion damages land resources and endangers human productivity and life, making it a key issue in global research on soil erosion nowadays. Gully headcut retreat (GHR) is the main form of gully erosion. Tiny concave features can be found in many retreating gully heads worldwide, and they are referred to as “niche terrain” in this study. To investigate the association between niche terrain and GHR, relevant research was reviewed on niches and stability analysis of gully heads with niches was modelled and analysed. Studies have shown that not all niches worldwide are identical due to regional differences in internal material–external environmental conditions. Special soil properties, joints, and cracks are the internal material conditions that lead to the formation of niche. External conditions include climate conditions, vegetation conditions, and topography. Water is the driving force for the formation of niche, while vegetation and topography are key factors. Niches can be regarded as the initial stage of GHR in areas where gully erosion is intense. In general, GHR is a composite cyclical process dominated by hydraulic erosion in the early stage and gravitational erosion in the late stage, including niche formation, inward concave formation, free face formation, overhanging soil collapse, and niche reformation. In this study, a model of gully head stability is applied, and it is found that the stability‐based factor of safety decreases exponentially with increasing niche height and crack depth, increases exponentially with increasing niche angle, and decreases quadratically with increasing catchment slope. Summarizing the common characteristics of niche terrains worldwide can facilitate the study of the evolution of gully erosion globally.
Shedding light on imaging safety: Decoding the origin of photocytotoxicity in RhB‐assisted fluorescence imaging
Authors: Luo Chaoqun , Yao Weiyun , Zhang Haolin , Jia Mingxuan , Lim Chang‐Keun , Hu Wenbo 
Published: April 2024

AbstractPhotocytotoxicity represents a significant limitation in the application of dye‐assisted fluorescence imaging (FI), often resulting in undesirable cellular damage or even cell death, thereby restricting their practical utility. The prevalence of Rhodamine B (RhB) in FI underscores the importance of elucidating its photocytotoxicity effects to minimize photodamage. This study identifies the primary cause of photocytotoxicity stems from the generation of cytotoxic singlet oxygen in RhB, utilizing femtosecond transient absorption spectroscopy coupled with quantum chemical calculations. The Laser power‐dependent cellular viability reveals a threshold at about 50 mW cm−2, surpassing which produces pronounced photocytotoxicity in vitro and in vivo. Notably, this threshold significantly falls below the safety limits (<200 mW cm−2) for laser use in health care, implying a huge risk of photodamage. This study provides valuable insights into the photocytotoxicity and offers essential guidelines for developing safer imaging protocols.
Do ECB's rate hikes have spillover effects on the Hungarian BUBOR and the EUR/HUF exchange rate? A five‐variable VAR model approach using the Diebold‐Yilmaz spillover table
Authors: Albert Molnar , Ágnes Csiszárik‐Kocsír 
Published: April 2024

AbstractWe intend to show the directional volatility spillovers between the European short term interbank lending rates (3‐month Euro Interbank Offered Rate [EURIBOR] and Euro Short‐Term Rate [ESTR]) and the Hungarian Budapest Interbank Offered Rate (BUBOR) and Euro‐Hungarian Forint exchange rate. To determine the extent to which the variables affect each other's volatilities we build a five‐variable vector autoregression (VAR) and determine the spillover table like in Diebold‐Yilmaz's 2012 work. This methodology is preferred to a simple impulse response function (IRF) because we manage to avoid the problem of non‐orthogonal innovations via the generalized forecast error variance decomposition framework. The issue of variable ordering, therefore, does not arise. We focus on three episodes of increased volatility in Hungarian and European short‐term interest rates: Q3–Q4 of 2019, Q1 of 2020 and Q3 of 2022. These episodes correspond to volatility spikes in EU markets that to some extent had a measurable spillover effect on Hungarian interbank rates. We find that on average, across the entire sample of 957 observations, about 6.3% of the volatility forecast error variance in all five European and Hungarian variables comes from spillovers. The total and directional spillovers over the sample are extremely low. We conclude that the European Central Bank's surprise policy decisions have a marginal impact on Hungarian interbank rates. We also find that BUBOR is primarily a net receiver of spillovers from the MAX short‐term government bond benchmark rather than the EURIBOR—this disproved our initial considerations.
Financial inclusion in India: How far do grassroots institutions matter?
Authors: Saravanabhavan Shika , Rajeev Meenakshi 
Published: April 2024

AbstractThough the relevance of grassroots institutions for financial inclusion (FI) is widely recognised, we still do not fully understand its differential effect on FI, particularly in relation to commercial banks. To investigate this issue, we consider the household's moneylender dependence as an indicator of financial exclusion and thus our outcome variable. Further, we have developed FI indices using indicators of commercial and cooperative banks, which we used as explanatory variables in our analysis. Our results show that, while there is a decreased dependence on moneylenders even at low levels of FI through cooperatives, commercial banks show an inverted U‐shaped relationship implying a decreasing effect only after a threshold level.
What do brain oscillations tell about the human sense of smell?
Authors: Mignot Coralie , Weise Susanne , Podlesek Dino , Leonhardt Georg , Bensafi Moustafa , Hummel Thomas 
Published: April 2024

AbstractBrain activity may manifest itself as oscillations which are repetitive rhythms of neuronal firing. These local field potentials can be measured via intracranial electroencephalography (iEEG). This review focuses on iEEG used to map human brain structures involved in olfaction. After presenting the methodology of the review, a summary of the brain structures involved in olfaction is given, followed by a review of the literature on human olfactory oscillations in different contexts. A single case is provided as an illustration of the olfactory oscillations. Overall, the timing and sequence of oscillations found in the different structures of the olfactory system seem to play an important role for olfactory perception.
Cognitive profiles of strategic decision‐makers: Implications for exploration–exploitation strategies
Authors: Vlašić Goran , Dabić Marina , Krupka Zoran 
Published: April 2024

AbstractOrganizational ambidexterity has long been in the focus of understanding how organizations address tensions between exploitation, which implies building new competencies in order to drive radical change, and exploitation, which implies building on top of existing competencies in order to deliver persistent incremental improvements. Research has shown that, at the organizational level, established incumbent organizations tend to avoid exploration. In this paper, we focus on understanding which cognitive profiles tend to get promoted to the highest management positions in established incumbent organizations. To address this research question, we used a data set on 176 key decision‐makers at five multinational organizations. Results indicate that inherent biases in promotion decisions at the highest levels of the established incumbent organizations favor pattern‐recognition cognitive profiles of managers, thus influencing organizational preference for exploitation over exploration. Results have implications for theory, explaining neurocognitive underpinnings of preference for exploitation in case of established incumbent organizations which arise from biases in promotional decisions; and for practice, implying the importance of debiasing promotion decisions to ensure organizational ability to deliver on explorative strategies, favoring innovations and new market creation.
Synthesis of 1,4‐dihydropyrrolo[3,2‐b]pyrrole‐containing donor–acceptor copolymers and their optoelectronic properties
Authors: Bell Kenneth‐John J. , Sabury Sina , Phan Vanessa , Wagner Ethan M. , Hawks Allison M. , Bartlett Kimberley A. , Collier Graham S. 
Published: April 2024

AbstractDonor–acceptor (D–A)‐conjugated polymers have achieved promising performance metrics in numerous optoelectronic applications that continue to motivate studying structure–property relationships and discovering new materials. Here, the materials toolbox is expanded by synthesizing D–A copolymers where 1,4‐dihydropyrrolo[3,2‐b]pyrrole (DHPP) is directly incorporated into the main chain of D–A copolymers for the first time via direct heteroarylation polymerization. Notably, the synthetic complexity of DHPP‐containing polymers coupled with thieno[3,2‐b]pyrrole‐4,6‐dione (TPD) or 3,6‐bis(2‐thienyl)‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione (Th2DPP) comonomers is calculated to be lower compared to many common conjugated polymers synthesized via direct arylation. The electron‐rich nature of DHPPs when coupled with TPD or DPP enables optoelectronic properties to be manipulated, evident by measuring distinctly different absorbance and redox properties. Additionally, these D–A copolymers demonstrate their potential in organic electronic applications, such as electrochromics and organic photovoltaics. The reported DHPP‐alt‐Th2DPP copolymer is the first DHPP‐based colored‐to‐transmissive electrochrome and achieves power conversion efficiencies of ~2.5% when incorporated into bulk heterojunction solar cells. Overall, the synthetic accessibility of DHPP monomers and their propensity to participate in robust polymerizations highlights the value of establishing structure–property relationships of an underutilized scaffold. These fundamental attributes serve to inform and advance efforts in the development of DHPP‐containing copolymers for various applications.