bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photocatalytic phosphine-mediated water activation for radical hydrogenation
Authors: Zhang Jingjing , Mück-Lichtenfeld Christian , Studer Armido 
Published: June 2023

AbstractThe chemical activation of water would allow this earth-abundant resource to be transferred into value-added compounds, and is a topic of keen interest in energy research1,2. Here, we demonstrate water activation with a photocatalytic phosphine-mediated radical process under mild conditions. This reaction generates a metal-free PR3–H2O radical cation intermediate, in which both hydrogen atoms are used in the subsequent chemical transformation through sequential heterolytic (H+) and homolytic (H•) cleavage of the two O–H bonds. The PR3–OH radical intermediate provides an ideal platform that mimics the reactivity of a ‘free’ hydrogen atom, and which can be directly transferred to closed-shell π systems, such as activated alkenes, unactivated alkenes, naphthalenes and quinoline derivatives. The resulting H adduct C radicals are eventually reduced by a thiol co-catalyst, leading to overall transfer hydrogenation of the π system, with the two H atoms of water ending up in the product. The thermodynamic driving force is the strong P=O bond formed in the phosphine oxide by-product. Experimental mechanistic studies and density functional theory calculations support the hydrogen atom transfer of the PR3–OH intermediate as a key step in the radical hydrogenation process.
Femtosecond proton transfer in urea solutions probed by X-ray spectroscopy
Authors: Yin Zhong , Chang Yi-Ping , Balčiūnas Tadas , Shakya Yashoj , Djorović Aleksa , Gaulier Geoffrey , Fazio Giuseppe , Santra Robin , Inhester Ludger , Wolf Jean-Pierre , Wörner Hans Jakob 
Published: June 2023

AbstractProton transfer is one of the most fundamental events in aqueous-phase chemistry and an emblematic case of coupled ultrafast electronic and structural dynamics1,2. Disentangling electronic and nuclear dynamics on the femtosecond timescales remains a formidable challenge, especially in the liquid phase, the natural environment of biochemical processes. Here we exploit the unique features of table-top water-window X-ray absorption spectroscopy3–6 to reveal femtosecond proton-transfer dynamics in ionized urea dimers in aqueous solution. Harnessing the element specificity and the site selectivity of X-ray absorption spectroscopy with the aid of ab initio quantum-mechanical and molecular-mechanics calculations, we show how, in addition to the proton transfer, the subsequent rearrangement of the urea dimer and the associated change of the electronic structure can be identified with site selectivity. These results establish the considerable potential of flat-jet, table-top X-ray absorption spectroscopy7,8 in elucidating solution-phase ultrafast dynamics in biomolecular systems.
Phase separation of FSP1 promotes ferroptosis
Authors: Nakamura Toshitaka , Hipp Clara , Santos Dias Mourão André , Borggräfe Jan , Aldrovandi Maceler , Henkelmann Bernhard , Wanninger Jonas , Mishima Eikan , Lytton Elena , Emler David , Proneth Bettina , Sattler Michael , Conrad Marcus 
Published: June 2023

AbstractFerroptosis is evolving as a highly promising approach to combat difficult-to-treat tumour entities including therapy-refractory and dedifferentiating cancers1–3. Recently, ferroptosis suppressor protein-1 (FSP1), along with extramitochondrial ubiquinone or exogenous vitamin K and NAD(P)H/H+ as an electron donor, has been identified as the second ferroptosis-suppressing system, which efficiently prevents lipid peroxidation independently of the cyst(e)ine–glutathione (GSH)–glutathione peroxidase 4 (GPX4) axis4–6. To develop FSP1 inhibitors as next-generation therapeutic ferroptosis inducers, here we performed a small molecule library screen and identified the compound class of 3-phenylquinazolinones (represented by icFSP1) as potent FSP1 inhibitors. We show that icFSP1, unlike iFSP1, the first described on-target FSP1 inhibitor5, does not competitively inhibit FSP1 enzyme activity, but instead triggers subcellular relocalization of FSP1 from the membrane and FSP1 condensation before ferroptosis induction, in synergism with GPX4 inhibition. icFSP1-induced FSP1 condensates show droplet-like properties consistent with phase separation, an emerging and widespread mechanism to modulate biological activity7. N-terminal myristoylation, distinct amino acid residues and intrinsically disordered, low-complexity regions in FSP1 were identified to be essential for FSP1-dependent phase separation in cells and in vitro. We further demonstrate that icFSP1 impairs tumour growth and induces FSP1 condensates in tumours in vivo. Hence, our results suggest that icFSP1 exhibits a unique mechanism of action and synergizes with ferroptosis-inducing agents to potentiate the ferroptotic cell death response, thus providing a rationale for targeting FSP1-dependent phase separation as an efficient anti-cancer therapy.
Single molecule infrared spectroscopy in the gas phase
Authors: Calvin Aaron , Eierman Scott , Peng Zeyun , Brzeczek Merrell , Satterthwaite Lincoln , Patterson David 
Published: June 2023

AbstractSpectroscopy is a key analytical tool that provides valuable insight into molecular structure and is widely used to identify chemical samples. Tagging spectroscopy is a form of action spectroscopy in which the absorption of a single photon by a molecular ion is detected via the loss of a weakly attached, inert ‘tag’ particle (for example, He, Ne, N2)1–3. The absorption spectrum is derived from the tag loss rate as a function of incident radiation frequency. So far, all spectroscopy of gas phase polyatomic molecules has been restricted to large molecular ensembles, thus complicating spectral interpretation by the presence of multiple chemical and isomeric species. Here we present a novel tagging spectroscopic scheme to analyse the purest possible sample: a single gas phase molecule. We demonstrate this technique with the measurement of the infrared spectrum of a single gas phase tropylium (C7H7+) molecular ion. The high sensitivity of our method revealed spectral features not previously observed using traditional tagging methods4. Our approach, in principle, enables analysis of multicomponent mixtures by identifying constituent molecules one at a time. Single molecule sensitivity extends action spectroscopy to rare samples, such as those of extraterrestrial origin5,6, or to reactive reaction intermediates formed at number densities that are too low for traditional action methods.
Influence of Ca doping in structural, electronic, optical and mechanical properties of Ba1−xCaxTiO3 perovskite from first-principles investigation
Authors: Hasan Zahid , Rahman M. Atikur , Das Dipta Kumar , Rouf Hasan Khaled 
Published: June 2023

AbstractNowadays, perovskite materials are well known for electronics and optoelectronics applications. We have investigated a potential candidate for those applications to compare the applicability in optoelectronics, photorefractive and photovoltaic (PV) devices. The systematic comparative study of the structural, electronic, optical, mechanical, and thermodynamic properties of pure BaTiO3and Ca doped BaTiO3(Ba1−xCaxTiO3where x = 0.125, 0.25, 0.375, 0.500, 0.625) perovskite have been carried out using first-principles and density-functional-theory calculations as recently this material was mostly experimented. The measured structural parameters from the geometrically optimized structure of cubic BT ceramic compared with the other theoretical values. A crystal phase transition occurs when doping content x = 0.25. The electronic band structure shows that the nature of the bandgap is changed from indirect bandgap to direct bandgap energy at G-point after doping the Ca atom into BaTiO3(BT) crystal. Doping of Ca into BT has led to bandstructure modification including conduction band (CB) shifting toward the higher energy level. Electronic properties have been reported to examine the contribution of different orbitals to the CB and to the valance band (VB). This study investigated the modification of optical properties such as absorption, reflectivity, refractive index, extinction coefficient, conductivity, dielectric function and loss function at the energy range from 0 to 30 eV. The prominent absorption peak and optical energy were observed at the UV light energy region. Based on the optical behavior of the material this theoretical research suggests that the doped BT solution is a suitable candidate for photorefractive and optoelectronic devices. Different elastic constants reveal mechanical stability and the existence of the covalent bond of those compounds. Debye temperature increases with doping content. Hence modification of BaTiO3crystal by Ca atom significantly develop various properties that led it to multifunctional applications.
An ethogram analysis of cutaneous thermal pain sensitivity and oxycodone reward-related behaviors in rats
Authors: Brice-Tutt Ariana C. , Montgomery Darrice S. , Kramer Cassidy M. , Novotny Peter M. , Malphurs Wendi L. , Sharma Abhisheak , Caudle Robert. M. , Bruijnzeel Adriaan W. , Setlow Barry , Neubert John K. , Murphy Niall P. 
Published: June 2023

AbstractInter-relationships between pain sensitivity, drug reward, and drug misuse are of considerable interest given that many analgesics exhibit misuse potential. Here we studied rats as they underwent a series of pain- and reward-related tests: cutaneous thermal reflex pain, induction and extinction of conditioned place preference to oxycodone (0.56 mg/kg), and finally the impact of neuropathic pain on reflex pain and reinstatement of conditioned place preference. Oxycodone induced a significant conditioned place preference that extinguished throughout repeated testing. Correlations identified of particular interest included an association between reflex pain and oxycodone-induced behavioral sensitization, and between rates of behavioral sensitization and extinction of conditioned place preference. Multidimensional scaling analysis followed by k-clustering identified three clusters: (1) reflex pain, rate of behavioral sensitization and rate of extinction of conditioned place preference (2) basal locomotion, locomotor habituation, acute oxycodone-stimulated locomotion and rate of change in reflex pain during repeated testing, and (3) magnitude of conditioned place preference. Nerve constriction injury markedly enhanced reflex pain but did not reinstate conditioned place preference. These results suggest that high rates of behavioral sensitization predicts faster rates of extinction of oxycodone seeking/reward, and suggest that cutaneous thermal reflex pain may be predictive of both.
A moment kernel machine for clinical data mining to inform medical decision making
Authors: Yu Yao-Chi , Zhang Wei , O’Gara David , Li Jr-Shin , Chang Su-Hsin 
Published: June 2023

AbstractMachine learning-aided medical decision making presents three major challenges: achieving model parsimony, ensuring credible predictions, and providing real-time recommendations with high computational efficiency. In this paper, we formulate medical decision making as a classification problem and develop a moment kernel machine (MKM) to tackle these challenges. The main idea of our approach is to treat the clinical data of each patient as a probability distribution and leverage moment representations of these distributions to build the MKM, which transforms the high-dimensional clinical data to low-dimensional representations while retaining essential information. We then apply this machine to various pre-surgical clinical datasets to predict surgical outcomes and inform medical decision making, which requires significantly less computational power and time for classification while yielding favorable performance compared to existing methods. Moreover, we utilize synthetic datasets to demonstrate that the developed moment-based data mining framework is robust to noise and missing data, and achieves model parsimony giving an efficient way to generate satisfactory predictions to aid personalized medical decision making.
Representational momentum of biological motion in full-body, point-light and single-dot displays
Authors: Zucchini Elena , Borzelli Daniele , Casile Antonino 
Published: June 2023

AbstractObserving the actions of others triggers, in our brain, an internal and automatic simulation of its unfolding in time. Here, we investigated whether the instantaneous internal representation of an observed action is modulated by the point of view under which an action is observed and the stimulus type. To this end, we motion captured the elliptical arm movement of a human actor and used these trajectories to animate a photorealistic avatar, a point-light stimulus or a single dot rendered either from an egocentric or an allocentric point of view. Crucially, the underlying physical characteristics of the movement were the same in all conditions. In a representational momentum paradigm, we then asked subjects to report the perceived last position of an observed movement at the moment in which the stimulus was randomly stopped. In all conditions, subjects tended to misremember the last configuration of the observed stimulus as being further forward than the veridical last showed position. This misrepresentation was however significantly smaller for full-body stimuli compared to point-light and single dot displays and it was not modulated by the point of view. It was also smaller when first-person full body stimuli were compared with a stimulus consisting of a solid shape moving with the same physical motion. We interpret these findings as evidence that full-body stimuli elicit a simulation process that is closer to the instantaneous veridical configuration of the observed movements while impoverished displays (both point-light and single-dot) elicit a prediction that is further forward in time. This simulation process seems to be independent from the point of view under which the actions are observed.
Strengths of social ties modulate brain computations for third-party punishment
Authors: Tang Zixuan , Qu Chen , Hu Yang , Benistant Julien , Moisan Frédéric , Derrington Edmund , Dreher Jean-Claude 
Published: June 2023

AbstractCostly punishment of social norm transgressors by third-parties has been considered as a decisive stage in the evolution of human cooperation. An important facet of social relationship knowledge concerns the strength of the social ties between individuals, as measured by social distance. Yet, it is unclear how the enforcement of social norms is influenced by the social distance between a third-party and a norm violator at the behavioral and the brain system levels. Here, we investigated how social distance between punishers and norm-violators influences third-party punishment. Participants as third-party punished norm violators more severely as social distance between them increased. Using model-based fMRI, we disentangled key computations contributing to third-party punishment: inequity aversion, social distance between participant and norm violator and integration of the cost to punish with these signals. Inequity aversion increased activity in the anterior cingulate cortex and bilateral insula, and processing social distance engaged a bilateral fronto-parietal cortex brain network. These two brain signals and the cost to punish were integrated in a subjective value signal of sanctions that modulated activity in the ventromedial prefrontal cortex. Together, our results reveal the neurocomputational underpinnings of third-party punishment and how social distance modulates enforcement of social norms in humans.
Glutamine synthetase (GS) knockout (KO) using CRISPR/Cpf1 diversely enhances selection efficiency of CHO cells expressing therapeutic antibodies
Authors: Srila Witsanu , Baumann Martina , Riedl Markus , Rangnoi Kuntalee , Borth Nicole , Yamabhai Montarop 
Published: June 2023

AbstractThe glutamine synthetase (GS)-based Chinese hamster ovary (CHO) selection system is an attractive approach to efficiently identify suitable clones in the cell line generation process for biologics manufacture, for which GS-knockout (GS-KO) CHO cell lines are commonly used. Since genome analysis indicated that there are two GS genes in CHO cells, deleting only 1 GS gene could potentially result in the activation of other GS genes, consequently reducing the selection efficiency. Therefore, in this study, both GS genes identified on chromosome 5 (GS5) and 1 (GS1) of CHO-S and CHO-K1, were deleted using CRISPR/Cpf1. Both single and double GS-KO CHO-S and K1 showed robust glutamine-dependent growth. Next, the engineered CHO cells were tested for their efficiency of selection of stable producers of two therapeutic antibodies. Analysis of pool cultures and subclones after a single round of 25 µM methionine sulfoxinime (MSX) selection indicated that for CHO-K1 the double GS5,1-KO was more efficient as in the case of a single GS5-KO the GS1 gene was upregulated. In CHO-S, on the other hand, with an autologously lower level of expression of both variants of GS, a single GS5-KO was more robust and already enabled selection of high producers. In conclusion, CRISPR/Cpf1 can be efficiently used to knock out GS genes from CHO cells. The study also indicates that for the generation of host cell lines for efficient selection, the initial characterisation of expression levels of the target gene as well as the identification of potential escape mechanisms is important.
Leveraging deep survival models to predict quality of care risk in diverse hospital readmissions
Authors: Tran Nhat Quang , Goel Gautam , Pudota Nirmala , Suesserman Michael , Helms John , Lasaga Daniel , Olson Dan , Bowen Edward , Bhattacharya Sanmitra 
Published: June 2023

AbstractHospital readmissions rate is reportedly high and has caused huge financial burden on health care systems in many countries. It is viewed as an important indicator of health care providers’ quality of care. We examine the use of machine learning-based survival analysis to assess quality of care risk in hospital readmissions. This study applies various survival models to explore the risk of hospital readmissions given patient demographics and their respective hospital discharges extracted from a health care claims dataset. We explore advanced feature representation techniques such as BioBERT and Node2Vec to encode high-dimensional diagnosis code features. To our knowledge, this study is the first to apply deep-learning based survival-analysis models for predicting hospital readmission risk agnostic of specific medical conditions and a fixed window for readmission. We found that modeling the time from discharge date to readmission date as a Weibull distribution as in the SparseDeepWeiSurv model yields the best discriminative power and calibration. In addition, embedding representations of the diagnosis codes do not contribute to improvement in model performance. We find dependency of each model’s performance on the time point at which it is evaluated. This time dependency of the models’ performance on the health care claims data may necessitate a different choice of model in quality of care issue detection at different points in time. We show the effectiveness of deep-learning based survival-analysis models in estimating the quality of care risk in hospital readmissions.
Long-term fungal inoculation of Ficus sycomorus and Tectona grandis woods with Aspergillus flavus and Penicillium chrysogenum
Authors: Mansour Maisa M. A. , Mohamed Wafaa A. , El-Settawy Ahmed A. A. , Böhm Martin , Salem Mohamed Z. M. , Farahat Marwa G. S. 
Published: June 2023

AbstractIn the current study, two molds, Aspergillus flavus (ACC# LC325160) and Penicillium chrysogenum (ACC# LC325162) were inoculated into two types of wood to be examined using scanning electron microscopy-energy dispersive X-ray (SEM–EDX) and computerized tomography (CT) scanning. Ficus sycomorus, a non-durable wood, and Tectona grandis, a durable wood, were the two wood blocks chosen, and they were inoculated with the two molds and incubated for 36 months at an ambient temperature of 27 ± 2 °C and 70 ± 5% relative humidity (RH). The surface and a 5-mm depth of inoculated wood blocks were histologically evaluated using SEM and CT images. The results showed that A. flavus and P. chrysogenum grew enormously on and inside of F. sycomorus wood blocks, but T. grandis wood displayed resistance to mold growth. The atomic percentages of C declined from 61.69% (control) to 59.33% in F. sycomorus wood samples inoculated with A. flavus while O increased from 37.81 to 39.59%. P. chrysogenum caused the C and O atomic percentages in F. sycomorus wood to drop to 58.43%, and 26.34%, respectively. C with atomic percentages in Teak wood’s C content fell from 70.85 to 54.16%, and 40.89%, after being inoculated with A. flavus and P. chrysogenum. The O atomic percentage rose from 28.78 to 45.19% and 52.43%, when inoculated with A. flavus and P. chrysogenum, respectively. Depending on how durable each wood was, The examined fungi were able to attack the two distinct types of wood in various deterioration patterns. T. grandis wood overtaken by the two molds under study appears to be a useful material for a variety of uses.
Influence of droplet size on the antibacterial efficacy of citral and citronella oil nanoemulsions in polysaccharide coated fresh-cut apples
Authors: Touayar Mounir , Zayani Rania , Messaoud Chokri , Salman Hesham 
Published: June 2023

AbstractFresh-cut fruits are highly perishable and susceptible to bacterial contamination. Polysaccharides edible coating loaded with essential oils nanoemulsions have the potential to extend shelf life and improve quality of fruits. The effectiveness of this approach is dependent on the properties of the nanoemulsions, such as droplet size (DS) and stability. This study aimed to optimize the production of citral (CT) and citronella oil (CTO) nanoemulsions (CT-CTO-NEs) incorporated in edible coating film to be used as natural antimicrobial agent in fresh-cut apples. After testing different combinations of surfactant (tween 80) and cosurfactant (propylene glycol) to obtain stable oil-in-water (o/w) nanoemulsions, the results demonstrated that optimized CT-CTO-NEs with DS less than 500 nm have been successfully achieved with high stability for 3 weeks at 4 °C. In addition, CT-CTO-NEs were obtained by In situ formation under magnetic stirring without applying complex high shear homogenization processes. Desired stability of CT-CTO-NEs also has been achieved within semi-solid matrix (sodium alginate cross-linked film). The relationship between DS and antibacterial activity was observed, with the smallest DS (< 100 nm) showing the highest antibacterial efficacy against Listeria monocytogenes and Escherichia coli. These results emphasize the importance of DS in the effectiveness of CT-CTO-NEs as an antibacterial coating for fresh-cut fruits.