bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photoinduced Metallonitrene Formation by N2 Elimination from Azide Diradical Ligands
Authors: Domenianni Luis I. , Bauer Markus , Schmidt‐Räntsch Till , Lindner Jörg , Schneider Sven , Vöhringer Peter 
Published: August 2023

AbstractTransition‐metal nitrides/nitrenes are highly promising reagents for catalytic nitrogen‐atom‐transfer reactivity. They are typically prepared in situ upon optically induced N2 elimination from azido precursors. A full exploitation of their catalytic potential, however, requires in‐depth knowledge of the primary photo‐induced processes and the structural/electronic factors mediating the N2 loss with birth of the terminal metal‐nitrogen core. Using femtosecond infrared spectroscopy, we elucidate here the primary molecular‐level mechanisms responsible for the formation of a unique platinum(II) nitrene with a triplet ground state from a closed‐shell platinum(II) azide precursor. The spectroscopic data in combination with quantum‐chemical calculations provide compelling evidence that product formation requires the initial occupation of a singlet excited state with an anionic azide diradical ligand that is bound to a low‐spin d8‐configured PtII ion. Subsequent intersystem crossing generates the Pt‐bound triplet azide diradical, which smoothly evolves into the triplet nitrene via N2 loss in a near barrierless adiabatic dissociation. Our data highlight the importance of the productive, N2‐releasing state possessing azide ππ* character as a design principle for accessing efficient N‐atom‐transfer catalysts.
A nitrogen‐rich DOPO‐based phosphoramide for improving the fire resistance of polycarbonate with comparable mechanical property
Authors: Cai Boyu , Jiang Qing , Xu Wendi , Wang Luze , Luo Zhonglin , Wang Biaobing 
Published: August 2023

AbstractA nitrogen‐rich DOPO‐based phosphoramide (DPAPZ) was synthesized using aminopyrazine and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) as raw materials, and blended with polycarbonate (PC) through melting method. The chemical structure of DPAPZ was validated by FTIR, 1H NMR and 31P NMR. The presence of DPAPZ endowed PC/DPAPZ composites with better fire safety and smoke suppression. With the incorporation of 6 wt% DPAPZ, PC/DPAPZ‐6 composite reached UL‐94 V‐0 rating and 30.2% of limiting oxygen index value. Simultaneously, the peak of heat release rate and total heat release of PC/DPAPZ‐6 were reduced by 44.8% and 47.0% as compared with the pure PC, respectively. The DPAPZ displayed bi‐phase flame retardant roles. In the gas phase, the decomposition of DPAPZ released phosphorus‐containing free radicals acting as the quencher of reactive H·/OH· and nonflammable NH3 diluting O2/combustible volatiles. In the condensed phase, the phosphorus‐containing components were dehydrated into metaphosphoric acid or polymetaphosphate covering the surface to protect the PC matrix from further combustion, and to promote the formation of a dense carbon layer to interrupt the transmission of O2 and volatiles between the combustion zone and the inner. The tensile strength of the composites displayed almost no change but the elongation at break decreased slightly with the addition of DPAPZ.
Fabrication ofAg2S‐incorporated polyamide thin film nanocomposite reverse osmosis membranes with antifouling properties
Authors: Nchoe Obakeng B. , Matshetshe Kabo , As' Ballim Muhammed , Tetyana Phumlani , Sikhwivhilu Keneiloe , Moloto Nosipho 
Published: August 2023

AbstractHerein we report on the fabrication of polyamide (PA) thin‐film composites (TFC) as reverse osmosis (RO) membranes with embedded silver sulfide (Ag2S) nanoparticles (NPs) to form thin‐film nanocomposites (TFN) and mitigate fouling. The fabrication of TFN membranes was done via interfacial polymerization on a polysulfone support membrane. Varied amounts of Ag2S NPs (20, 30, and 50 mg) were added to the aqueous phase to form membranes with enhanced antifouling and permselectivity performance. The chemical composition, surface topography, resistance to organic fouling and biofouling, water flux, and salt rejection, were tested on all membranes. The formation of Ag2S was confirmed by XRD and transmission electron microscopy. The pure water flux (Jo) obtained by all TFN membranes was above 25 L/m2h. Moreover, the 30 mg loaded TFN membrane attained the highestJoof 32.7 L/m2h. Salt rejection of the nanocomposite membranes were observed to be above 98%, which deems them suitable materials for desalination. TFN demonstrated resistance to fouling by bovine serum albumin and was able to retard bacterial colony formation. This was attributed to antibacterial properties of Ag2S NPs. Moreover, surface roughness decreased with increased NP loading, which also reduced the propensity of fouling.
Designing Magnetic Properties in CrSBr through Hydrostatic Pressure and Ligand Substitution
Authors: Telford Evan J. , Chica Daniel G. , Ziebel Michael E. , Xie Kaichen , Manganaro Nicholas S. , Huang Chun‐Ying , Cox Jordan , Dismukes Avalon H. , Zhu Xiaoyang , Walsh James P. S. , Cao Ting , Dean Cory R. , Roy Xavier 
Published: August 2023

AbstractMagnetic van der Waals (vdW) materials are a promising platform for producing atomically thin spintronic and optoelectronic devices. The A‐type antiferromagnet CrSBr has emerged as a particularly exciting material due to its high magnetic ordering temperature, semiconducting electrical properties, and enhanced chemical stability compared to other vdW magnets. Exploring mechanisms to tune its magnetic properties will facilitate the development of nanoscale devices based on vdW materials with designer magnetic properties. Here it is investigated how the magnetic properties of CrSBr change under pressure and ligand substitution. Pressure compresses the unit cell, increasing the interlayer exchange energy while lowering the Néel temperature. Ligand substitution, realized synthetically through Cl alloying, anisotropically compresses the unit cell and suppresses the Cr‐halogen covalency, reducing the magnetocrystalline anisotropy energy and decreasing the Néel temperature. A detailed structural analysis combined with first‐principles calculations reveals that alterations in the magnetic properties are intricately related to changes in direct Cr–Cr exchange interactions and the Cr–anion superexchange pathways. Further, it is demonstrated that Cl alloying enables chemical tuning of the interlayer coupling from antiferromagnetic to ferromagnetic, which is unique among known two‐dimensional magnets.
Melon and rostral muscle morphology of Gervais' beaked whale (Mesoplodon europaeus): Alternating patterns of bilateral asymmetry
Authors: Denk Michael , McLellan William , Pabst D. Ann , Rommel Sentiel , Keenan Tiffany , Sharp Sarah , Niemeyer Misty , Hunter Nicole , Block Gary , Nelson Nathan , Harms Craig , Thornton Steven , Costidis Alexander , Moore Michael 
Published: August 2023

AbstractToothed whales utilize specialized nasal structures such as the lipid‐rich melon to produce sound and propagate it into the aquatic environment. Very little nasal morphology of mesoplodont beaked whales has been described in the literature, and the anatomy of the melon and associated musculature of Gervais' beaked whale (Mesoplodon europaeus) remains undescribed. Heads of three (n = 3) Gervais' beaked whales were examined in detail via dissection as well as computed tomography (CT) and magnetic resonance imaging (MRI). Two additional Gervais' beaked whale individuals (n = 2) were studied via archived CT and MRI scans. Representative transverse dissection sections of the melon were processed for polarized light imaging to verify the presence of tendons inserting into the melon tissue. Three‐dimensional (3D) CT reconstructions of the melon, rostral muscles, and associated structures were performed to assess morphology and spatial relationships. In all individuals, the melon's main body demonstrated a bilaterally asymmetrical, curvilinear geometry. This curvilinear shape was defined by a pattern of alternating asymmetry in the medial rostral muscles that projected into the melon's tissue. In transverse polarized light imaging, a network of tendons originating from these asymmetrical rostral muscle projections was observed permeating the melon's lipid tissue. This curvilinear melon morphology and associated asymmetrical musculature suggest a means of lengthening the lipid pathway within a relatively short dimensional footprint. In addition, the species‐specific arrangement of muscular projections suggests complex fine‐tuning of the melon's geometry during echolocation. Further studies may lend additional insight into the function of this unusual melon morphology.
Facts in the machine: Systems of record and the performance of sociotechnical truth
Authors: Hauser Elliott 
Published: August 2023

AbstractInformation systems serve as the “source of truth” for much of social reality, from credit scores to eligibility for boarding an airplane to the current time. In contexts of practical consensus, the system makes it so. I label this phenomenon system‐dependent truth. This paper advances a theory of performative truthmaking, wherein the agencies of giving as and taking as produce facts and truth as relations. I introduce the term systems of record to denote information systems that contain facts rather than propositions. I develop a suitable performative approach to the phenomenon of system‐dependent truth by synthesizing John Searle's social ontology, an account of truth, facts, and social reality, with Karen Barad's agential realism, an onto‐epistemology of human and nonhuman agency. Using several specific examples drawn from travel and migration contexts, including the US government's No Fly List, I show that system‐dependent truth arises when an agent takes information from a system as fact during the performance of sociotechnical truth. I argue that the agencies of truthmaking and factmaking are a distinct form of power, that the coordination of these agencies constitutes institutional rationalities of potentially global scale, and that systems of record are therefore critical sites for justice‐oriented information studies.
Empathy deficits, callous‐unemotional traits and structural underpinnings in autism spectrum disorder and conduct disorder youth
Authors: Tkalcec Antonia , Bierlein Maria , Seeger‐Schneider Gudrun , Walitza Susanne , Jenny Bettina , Menks Willeke M. , Felhbaum Lynn V. , Borbas Reka , Cole David M. , Raschle Nora , Herbrecht Evelyn , Stadler Christina , Cubillo Ana 
Published: August 2023

AbstractDistinct empathy deficits are often described in patients with conduct disorder (CD) and autism spectrum disorder (ASD) yet their neural underpinnings and the influence of comorbid Callous‐Unemotional (CU) traits are unclear. This study compares the cognitive (CE) and affective empathy (AE) abilities of youth with CD and ASD, their potential neuroanatomical correlates, and the influence of CU traits on empathy. Adolescents and parents/caregivers completed empathy questionnaires (N = 148 adolescents, mean age = 15.16 years) and T1 weighted images were obtained from a subsample (N = 130). Group differences in empathy and the influence of CU traits were investigated using Bayesian analyses and Voxel‐Based Morphometry with Threshold‐Free Cluster Enhancement focusing on regions involved in AE (insula, amygdala, inferior frontal gyrus and cingulate cortex) and CE processes (ventromedial prefrontal cortex, temporoparietal junction, superior temporal gyrus, and precuneus). The ASD group showed lower parent‐reported AE and CE scores and lower self‐reported CE scores while the CD group showed lower parent‐reported CE scores than controls. When accounting for the influence of CU traits no AE deficits in ASD and CE deficits in CD were found, but CE deficits in ASD remained. Across all participants, CU traits were negatively associated with gray matter volumes in anterior cingulate which extends into the mid cingulate, ventromedial prefrontal cortex, and precuneus. Thus, although co‐occurring CU traits have been linked to global empathy deficits in reports and underlying brain structures, its influence on empathy aspects might be disorder‐specific. Investigating the subdimensions of empathy may therefore help to identify disorder‐specific empathy deficits.
A universal surrogate matrix assay for urea measurement in clinical pharmacokinetic studies of respiratory diseases
Authors: Tang Yang , Van Parys Michael , Walker Abigail , Drelick Alexandra , Liang Xiaorong , Dean Brian , Chen Liuxi 
Published: August 2023

AbstractIn pharmacokinetic studies for respiratory diseases, urea is a commonly used dilution marker for volume normalization of various biological matrices, owing to the fact that urea diffuses freely throughout the body and is minimally affected by disease states. In this study, we developed a convenient liquid chromatography–tandem mass spectrometry (LC–MS/MS) surrogate matrix assay for accurate urea quantitation in plasma, serum and epithelial lining fluid. Different mass spectrometer platforms and ionization modes were compared in parallel. The LC method and mass spectrometer parameters were comprehensively optimized to reduce interferences, to smooth the baseline and to maximize the signal‐to‐noise ratio. Saline was selected as the surrogate matrix, and its suitability was confirmed by good parallelism and accurate quality control sample measurements. Reliable and robust assay performance was demonstrated by precision and accuracy, dilution integrity, sensitivity, recovery and stability, all of which met bioanalysis requirements to support clinical studies. The assay performance was also verified and better understood by comparing it with a colorimetric assay and to a surrogate analyte assay. The newly developed surrogate matrix assay has the potential to be further expanded for urea quantitation in numerous physiological matrices.
Accelerometer‐derived sleep measures in idiopathic dystonia: A UK Biobank cohort study
Authors: Bailey Grace A , Wadon Megan E. , Komarzynski Sandra , Matthews Clare , Davies Elin Haf , Peall Kathryn J. 
Published: August 2023

AbstractBackgroundSleep disturbance is an increasingly recognized non‐motor trait in dystonia, with varying findings reported to date. Here, we examine sleep in a UK Biobank derived dystonia cohort using subjective self‐reported sleep symptoms and objective accelerometer‐derived sleep measures, with comparison to a control population.MethodsA total of 241 dystonia cases were compared to 964 matched controls in analysis of self‐reported sleep symptoms and changes in sleep architecture using wrist‐worn triaxial accelerometers.ResultsDystonia participants had poorer self‐reported sleep patterns compared to controls. Accelerometery measurements demonstrated later sleep times, reduced time in bed, and shifts in circadian rhythm. No association was observed with pain, and only limited relationships with psychiatric symptoms.DiscussionThis study demonstrates the utility of accelerometers in longer term evaluation of sleep in dystonia, for measurement of disturbance and response to treatment. Compared to controls, altered sleep and circadian rhythm were more common in dystonia patients which may contribute to the clinical phenotype.
Establishment of a facial nerve trunk crush injury model and evaluation of facial nerve self‐healing in rats
Authors: Fei Jing , Guan Xirui , Gao Lin , Ni Ping , Zheng Hongdi , Duan Kunling , Liao Na , Li Leiji 
Published: August 2023

AbstractIntroduction/aimsTo facilitate further investigation into the mechanisms of facial nerve regeneration, a simple and reliable model of facial nerve crush injury is essential. Nevertheless, the establishment of such models lacks standardization and repeatability, while the healing capacity of the nerve is often overlooked, potentially affecting future studies.MethodsWe made facial nerve trunk crush injury models with different pressing times and detected the changes from the distal nerves to the motoneurons via behavior analysis, electrophysiological test, and histomorphometry analysis.ResultsIt revealed a particular capacity for self‐healing following facial nerve crush damage because there was almost no facial motoneuron apoptosis in the MC group during the observation period, and rats in MC group had total facial paralysis in behavioral tests following surgery and varying degrees of recovery 28 days postoperatively with no treatments. As the pressing time increased, the latency, wave amplitude, nerve fiber damage degree, nerve axon ratio, myelin thickness, electroneurograph (ENoG) value, ultrastructural damage, abnormal morphological changes, and the buccal muscle atrophy of each MC group gradually increased or got worse during the observation period. However, after 28 postoperative days, only the ENoG values of the M10min and M12min groups were beyond 90%, indicating no self‐healing.DiscussionIt suggests that a stable model of peripheral facial palsy may be created by applying a 12.5 cm mosquito clamped to the facial nerve trunk for at least 10 min, which laid the foundation for the subsequent research to objectively evaluate facial nerve regeneration.
Sustainable business models for smallholder farmers: Challenges for and lessons from theBarshapump experience
Authors: Intriago Zambrano Juan Carlo , Diehl Jan‐Carel , Ertsen Maurits W. 
Published: August 2023

AbstractSmallholder farmers (SFs) are cornerstone actors in eradicating poverty and hunger. Companies have recently focused on SFs as potential customers and suppliers. Several hindrances yet prevent SFs to be commercially viable actors. In this respect, sustainable business models (SBMs) bring opportunities for companies to increase profit, improve SFs' livelihoods, and promote environmental sustainability. Recognizing these opportunities, the Dutch company aQysta provides the Barsha pump (BP) as a sustainable irrigation solution for SFs. The challenges for BP adoption that remain for SFs illustrate that there is still limited understanding of how SBMs can support companies in engaging with SFs. To expand this understanding, we conducted a multiple‐case analysis of 10 organizations providing SF‐tailored products and/or services. Based on this analysis, we have drawn lessons for aQysta (and similar companies) to improve the BP's value proposition and we elaborate on the implications of this study for other organizations engaging commercially with SFs.
Expectations and beyond: The nexus of AI instrumentality and brand credibility in voice assistant retention using extended expectation‐confirmation model
Authors: Ghazali Ezlika , Mutum Dilip S. , Lun Na Kai 
Published: August 2023

AbstractAI‐based voice assistants (AIVA) are capable of interpreting human speech and responding with useful information, aiding with tasks, and controlling other devices. The usage of these AIVAs has grown significantly worldwide. Despite this growth, studies on user behavior related to continued usage intention of AIVAs and effects on the long‐term commercial sustainability of brands, remain low. What is less understood is the potential of AI instrumentality attributes and brand credibility components in provoking shifts in post‐use behavior of AIVAs. This study proposes a model which expands on the Expectation‐Confirmation Model for user continuance behavior of AIVAs, by integrating user's technology related traits, AI instrumentality attributes and brand credibility. To verify the research hypotheses, the study employed partial least square—structural equation modelling, based on 281 validated responses of a survey. This study highlights the significance of Optimism, Innovativeness, and Discomfort for post‐adoption confirmation. Higher post‐adoption confirmation is strongly associated with perceived intelligence, anthropomorphism, information quality, and system quality. Anthropomorphism and information quality are key factors for brand expertise, while anthropomorphism and system quality are significant for brand trustworthiness. The study confirms that brand expertise and trustworthiness lead to post‐use satisfaction and use continuance intention. Understanding the antecedents of satisfaction and continuance intention extends the existing literature on AIVAs and provides valuable insights for academics and practitioners alike. Some implications for researchers and managers are discussed.
Citrus Honeys from Three Different Regions of Turkey: HPLC‐DAD Profiling and in Vitro Enzyme Inhibition, Antioxidant, Anti‐Inflammatory and Antimicrobial Properties with Chemometric Study
Authors: Tel‐Çayan Gülsen , Çiftçi Begüm Hazar , Taş‐Küçükaydın Meltem , Temel Yeşim , Çayan Fatih , Küçükaydın Selçuk , Duru Mehmet Emin 
Published: August 2023

AbstractThe objectives of the present study are to compare the phenolic profiles and biological activities of 15 citrus honey samples from three different locations in Turkey using a chemometric approach. The HPLC‐DAD analysis was used to determine phenolic profiles. Nineteen phenolic compounds were identified. Gallic acid (107.14–717.04 μg/g) was recorded as the predominant compound. AF (Antalya‐Finike) had the highest antioxidant activity in ABTS⋅+ (IC50: 18.01±0.69 mg/mL), metal chelating (IC50: 6.20±0.19 mg/mL) and CUPRAC (A0.50: 12.05±0.68 mg/mL) assays, while it revealed the best anti‐inflammatory activity against COX‐2 (17.28±0.22 %) and COX‐1 (43.28±0.91 %). AM (Antalya‐Manavgat) was the most active in β‐carotene‐linoleic acid (IC50: 10.05±0.19 mg/mL), anti‐urease (38.90±0.69 %), anti‐quorum sensing and antimicrobial activities. AKO1 (Adana‐Kozan‐1) in DPPH⋅ (IC50: 34.25±0.81 mg/mL) assay, AKU1 (Antalya‐Kumluca‐1) in tyrosinase inhibition activity (37.73±0.38 %) assay, AKU2 (Antalya‐Kumluca‐2) in AChE (10.55±0.63 %) and BChE (9.18±0.45 %) inhibition activity assays showed the best activity. Chemometric tools were applied to the phenolic compositions and biological properties. PCA and HCA ensured that 15 citrus honey samples were grouped into 3 clusters. The results showed that myricetin, kaempferol, vanillin, protocatechuic acid, rosmarinic acid, rutin, vanillic acid, gallic acid, catechin and p‐hydroxyphenyl acetic acid are phenolic compounds that can be used in the classification of citrus honeys.
Nucleoside‐Driven Specificity of DNA Methyltransferase**
Authors: Gade Madhuri , Gardner Jasmine M. , Jain Prashant , Laurino Paola 
Published: August 2023

AbstractWe have studied the adenosine binding specificities of two bacterial DNA methyltransferases, Taq methyltransferase (M.TaqI), and HhaI methyltransferase (M.HhaI). While they have similar cofactor binding pocket interactions, experimental data showed different specificity for novel S‐nucleobase‐l‐methionine cofactors (SNMs; N=guanosyl, cytidyl, uridyl). Protein dynamics corroborate the experimental data on the cofactor specificities. For M.TaqI the specificity for S‐adenosyl‐l‐methionine (SAM) is governed by the tight binding on the nucleoside part of the cofactor, while for M.HhaI the degree of freedom of the nucleoside chain allows the acceptance of other bases. The experimental data prove catalytically productive methylation by the M.HhaI binding pocket for all the SNMs. Our results suggest a new route for successful design of unnatural SNM analogues for methyltransferases as a tool for cofactor engineering.