bluuebunny/crossref_metadata_2025_split huggingface dataset:
Elucidation of the Charging Mechanisms and the Coupled Structural–Mechanical Behavior of Ti3C2Tx (MXenes) Electrodes by In Situ Techniques
Authors: Bergman Gil , Ballas Elad , Gao Qiang , Nimkar Amey , Gavriel Bar , Levi Mikhael D. , Sharon Daniel , Malchik Fyodor , Wang Xuehang , Shpigel Netanel , Mandler Daniel , Aurbach Doron 
Published: January 2023

AbstractThe discovery of the Ti3C2Tx compounds (MXenes) a decade ago opened new research directions and valuable opportunities for high‐rate energy storage applications. The unique ability of the MXenes to host various mono‐ and multivalent cations and their high stability in different electrolyte environments including aqueous, organic, and ionic liquid solutions, promoted the rapid development of advanced MXene‐based electrodes for a large variety of applications. Unlike the vast majority of typical intercalation compounds, the electrochemical performance of MXene electrodes is strongly influenced by the presence of co‐inserted solvent molecules, which cannot be detected by conventional current/potential electrochemical measurements. Furthermore, the electrochemical insertion of ions into MXene interspaces results in strong coupling with the intercalation‐induced structural, dimensional, and viscoelastic changes in the polarized MXene electrodes. To shed light on the charging mechanisms of MXene systems and their associated phenomena, the use of a large variety of real‐time monitoring techniques has been proposed in recent years. This review summarizes the most essential findings related to the charging mechanism of Ti3C2Tx electrodes and their potential induced structural and mechanical phenomena obtained by in situ investigations.
A Photoacoustic Probe with Blood‐Brain Barrier Crossing Ability for Imaging Oxidative Stress Dynamics in the Mouse Brain
Authors: Cui Yijing , Wang Xiaoqing , Jiang Zhiyong , Zhang Changli , Liang Zhaolun , Chen Yuncong , Liu Zhipeng , Guo Zijian 
Published: January 2023

AbstractSpatiotemporal assessment of the oxidative stress dynamics in the brain is crucial for understanding the molecular mechanism underlying neurodegenerative diseases. However, existing oxidative stress probes have poor blood‐brain barrier permeability or poor penetration depth, making them unsuitable for brain imaging. Herein, we developed a photoacoustic probe that enables real‐time imaging of oxidative stress dynamics in the mouse brain. The probe not only responds to oxidative stress in a reversible and ratiometric manner, but it can also cross the blood‐brain barrier of the mouse brain. Notably, the probe displayed excellent photoacoustic imaging of oxidative stress dynamics in the brains of Parkinson's disease mouse models. In addition, we investigated the antioxidant properties of natural polyphenols in the brain of a Parkinson's disease mouse model using the probe as an imaging agent and suggested the potential of the probe for screening anti‐oxidative stress agents.
A Convergent, Modular Approach to Trifluoromethyl‐Bearing 5‐Membered Rings via Catalytic C(sp3)−H Activation
Authors: Wu Kai , Zhang Xuyang , Wu Liang‐Liang , Huang Jie‐Sheng , Che Chi‐Ming 
Published: January 2023

AbstractTrifluoromethyl‐bearing 5‐membered rings are prevalent in bioactive molecules, but modular approaches to these compounds by functionalization of robust C(sp3)−H bonds in a direct and selective manner are extremely challenging. Herein we report the rhodium‐catalyzed α‐CF3‐α‐alkyl carbene insertion into C(sp3)−H bonds of a broad range of substrates to access 7 types of CF3‐bearing saturated 5‐membered carbo‐ and heterocycles. The reaction is particularly effective for benzylic C−H insertion exerting good site‐, diastereo‐ and enantiocontrol, and applicable to the synthesis of chiral CF3 analogues of bioactive molecules. Ruthenium α‐CF3‐α‐alkyl carbene complexes underwent stoichiometric reactions to give C−H insertion products, lending evidence for the involvement of metal α‐CF3‐α‐alkyl carbene species in the catalytic cycle. DFT calculations revealed that the π⋅⋅⋅π attraction and intra‐carbene C−H⋅⋅⋅F hydrogen bond elucidate the origin of selectivity of the benzylic C−H insertion reactions.
Metalla‐Claisen Rearrangement in Gold‐Catalyzed [4+2] Reaction: A New Elementary Reaction Suggested for Future Reaction Design
Authors: Liu Jing , Yang Yusheng , Shi Weiming , Yu Zhi‐Xiang 
Published: January 2023

AbstractWe report here computational evidence for a metalla‐Claisen rearrangement (MCR) in the case of gold‐catalyzed [4+2] cycloaddition reaction of yne‐dienes. The [4+2] reaction starts from exo cyclopropanation, followed by MCR and reductive elimination. The cyclopropane moiety formed in the first step is crucial for a low barrier of the MCR step. In addition, the importance of an appropriate combination of the tether group and the terminal substituent on alkyne in the yne‐diene substrates was studied. The mechanism of rhodium‐catalyzed [4+2] reaction of yne‐dienes was also investigated to see whether an MCR mechanism is involved or not. The findings and new understanding hereby reported represent an important advance in the catalysis field.
Perylene‐Based Reactive Oxygen Species Supergenerator for Immunogenic Photochemotherapy against Hypoxic Tumors
Authors: Lou Xue , Wang Hui , Liu Yu , Huang Yongwei , Liu Zhonghua , Zhang Wei , Wang Tie 
Published: January 2023

AbstractReactive oxygen species (ROS) can act as cytotoxic radicals to directly kill tumor cells and concurrently trigger immunogenic cell death (ICD) to efficiently achieve tumor therapy. Thus motivated, we herein present one perylene monoamide‐based ROS supergenerator (PMIC‐NC) that not only induces hypoxia‐enhanced Type‐I ROS burst aided by proton transients but also triggers Type‐I/II ROS production by electron or energy transfer under near‐infrared (NIR) light irradiation and also elicits a strong ICD effect. More interesting, the mitochondria‐ and lung‐specific distribution of PMIC‐NC also boosts the tumor therapeutic efficiency. As a result, PMIC‐NC was employed for NIR‐triggered photodynamic therapy, hypoxia‐enhanced chemotherapy and also displayed robust immunogenicity for systemic tumor eradication. This work thus contributes one proof‐of‐concept demonstration of perylene as an integrated therapeutic platform for efficient immunogenic photochemotherapy against hypoxic tumors.
Phylogenomic analysis of Syrphoidea (Diptera: Syrphidae, Pipunculidae) based on the expanded mitogenomic data
Authors: Guo Shibao , Chen Junhua , Song Nan 
Published: January 2023

AbstractThe mitochondrial genome has become the most widely used genomic resource in resolving the insect phylogenetic relationships. In this study, we assess the interrelationships among the syrphid and pipunculid members of Syrphoidea using mitochondrial genome sequences of 152 taxa, 9 of which are newly reported and three are assembled from the existing transcriptome data. The Pipunculidae was found to be deeply nested members of Schizophora, which resulted in a nonmonophyletic Syrphoidea. In the monophyletic Syrphidae, unequivocal robust support was found for Microdontinae as the sister group of all other Syrphidae. The subfamily Eristalinae was nonmonophyletic. The Pipizinae was recovered as the sister group to the Syrphinae, albeit with strong support. As a whole, our results are concord with previously established hypotheses on Syrphoidea from the genome scale data. The mitochondrial genomes were successful in producing a robustly supported phylogenetic framework for the Syrphoidea.
Influence of cosmic rays on environmental ecosystems
Authors: Rodríguez‐López Lien , González‐Rodríguez Lisdelys , Díaz‐García Tayra , Cardenas Rolando 
Published: January 2023

AbstractIt is presented a model to consider the effect of high energy cosmic rays on three types of terrestrial ecosystem: coastal macroalgae, lakes, and forests. The model includes insights into muon dosimetry based in the stopping power of muons while traveling in water and soft biological tissues. It is shown that a muon from secondary cosmic rays could deposit in cells an energy much higher than that deposited by ultraviolet photons coming from the Sun. Consequently, drastic short‐term reductions of photosynthesis are obtained if energetic astrophysical phenomena such as gamma ray bursts and neutron star mergers happen in our astronomical neighborhood, while radiational solar storms also cause considerable inhibition of photosynthesis.
Design, Synthesis, and Antimycobacterial Evaluation of Novel Tetrahydroisoquinoline Hydrazide Analogs
Authors: Kumar Boddupalli Venkata Siva , Khetmalis Yogesh Mahadu , Nandikolla Adinarayana , Kumar Banoth Karan , Van Calster Kevin , Murugesan Sankaranarayanan , Cappoen Davie , Sekhar Kondapalli Venkata Gowri Chandra 
Published: January 2023

AbstractA series of novel 2‐substituted‐5,7‐dichloro‐1,2,3,4‐tetrahydroisoquinoline‐6‐carbohydrazide were designed, synthesized and structures were confirmed by analytical methods, viz., 1H‐NMR, 13C‐NMR and Mass spectrometry. Synthesized derivatives were evaluated for their anti‐mycobacterial activity against Mycobacterium tuberculosis (Mtb) H37Ra. Among all the evaluated compounds, 10A25 containing biphenyl moiety exhibited significant inhibition with IC50 4.7 μM. 10A19, with an electron‐withdrawing Iodo group in the ortho position of the phenyl exhibited significant anti‐tubercular activity with IC50 8.8 μM. IC50 values of the remaining compounds ranged from 9.2 to 73.6 μM. Molecular docking study of the significantly active compound 10A25 was performed to determine the putative binding position of the test ligand at the active site of the selected target proteins Mycobacterium tuberculosis enoyl reductase (InhA) PDB – 4TZK and peptide deformylase PDB – 3E3U. A suitable single crystal for one of the active compounds, 10A12, was generated and analysed to further confirm the structure of the compounds.
Understanding the Interactions of Guanine Quadruplexes with Peptides as Novel Strategies for Diagnosis or Tuning Biological Functions
Authors: Miclot Tom , Froux Aurane , D'Anna Luisa , Bignon Emmanuelle , Grandemange Stéphanie , Barone Giampaolo , Monari Antonio , Terenzi Alessio 
Published: January 2023

AbstractGuanine quadruplexes (G4s) are nucleic acid structures exhibiting a complex structural behavior and exerting crucial biological functions in both cells and viruses. The specific interactions of peptides with G4s, as well as an understanding of the factors driving the specific recognition are important for the rational design of both therapeutic and diagnostic agents. In this review, we examine the most important studies dealing with the interactions between G4s and peptides, highlighting the strengths and limitations of current analytic approaches. We also show how the combined use of high‐level molecular simulation techniques and experimental spectroscopy is the best avenue to design specifically tuned and selective peptides, thus leading to the control of important biological functions.
Effect of UV Stress on the Structure and Function of Pro‐apoptotic Bid and Anti‐apoptotic Bcl‐xl proteins
Authors: Bera Akash , Singh Suraj , D'Souza Jacinta S. , Hosur Ramakrishna V. , Mishra Pushpa 
Published: January 2023

AbstractUltraviolet C (UV‐C) radiation induces apoptosis in mammalian cells via the mitochondrion‐mediated pathway. The Bcl‐2 family of proteins are the regulators of the mitochondrial pathway of apoptosis and appears responsive to UV‐C radiation. It is unknown how the structure and, effectively, the function of these proteins are directly impacted by UV‐C exposure. Here, we present the effect of UV‐C irradiation on the structure and function of pro‐apoptotic Bid‐FL and anti‐apoptotic Bcl‐xlΔC proteins. Using a variety of biophysical tools, we show that, following UV‐C irradiation, the structures of Bcl‐xlΔC and Bid‐FL are irreversibly altered. Bcl‐xLΔC is found to be more sensitive to UV stress than Bid‐FL Interestingly, UV‐C exposure shows dramatic chemical shift perturbations in consequence of dramatic structural perturbations (α‐helix to β‐sheet) in the BH3‐ binding region, a crucial segment of Bcl‐xlΔC. Furter it has been shown that UV‐exposed Bcl‐xlΔC has reduced efficacy of its interactions with pro‐apoptotic tBid.
Flumatinib plus venetoclax as an effective therapy for Philadelphia chromosome‐positive acute myeloid leukemia: A case report
Authors: Huang Si‐Man , Tao Tao , Wan Chao‐Ling , Wu Tian‐Mei , Cao Han‐Yu , Qiu Yan , Shen Xiang‐Dong , Wang Bin‐Ru , Ge Shuai‐Shuai , Li Yan‐Yan , Zhang Tong‐Tong , Wu Bing , Xue Sheng‐Li 
Published: January 2023

AbstractPhiladelphia chromosome‐positive acute myeloid leukemia (Ph + AML) is a rare type of AML with a low survival rate and poor prognosis. We first report a Ph + AML patient who remained in long‐term remission after the combination of flumatinib and venetoclax, which could provide corresponding treatment ideas for clinical practice.
Treatment of a high healthcare utilizer with sepsis in a virtual hybrid hospital‐at‐home program
Authors: Paulson Margaret R. , Torres‐Guzman Ricardo A. , Matcha Gautam V. , Avila Francisco R. , Maita Karla C. , Garcia John P. , Forte Antonio J. , Maniaci Michael J. 
Published: January 2023

AbstractHigh healthcare utilizers are often chronically ill patients who require aggressive hospital and outpatient care. We describe a patient with septic shock who was stabilized in the intensive care unit, then transitioned to a virtual hybrid hospital‐at‐home to complete both inpatient care as well as outpatient wound and rehabilitation therapy.
IrO2/Ir Composite Nanoparticles (IrO2@Ir) Supported on TiNxOy Coated TiN: Efficient and Robust Oxygen Evolution Reaction Catalyst for Water Electrolysis
Authors: Karade Swapnil Sanjay , Sharma Raghunandan , Gyergyek Saso , Morgen Per , Andersen Shuang Ma 
Published: January 2023

AbstractIt is crucial but challenging to reduce the required noble‐metal loading without compromising the catalytic performance of oxygen evolution reaction (OER) catalysts. This study presents a highly active OER catalyst composed of IrO2 with Ir rich surface (IrO2@Ir) nanoparticles supported over nano TiN coated with TiOxNy (IrO2@Ir/TiN). The present approach demonstrates superior OER catalysts with high activity through small, uniformly dispersed IrO2@Ir nanoparticles, along with high durability owing to robust catalyst support and strong catalyst‐support interaction. The synthesized IrO2@Ir/TiN with an Ir loading of 40 wt % exhibits a mass‐normalized OER activity of 637 AgIr−1, which is 2.4 times that of the unsupported commercial benchmark IrO2 OER electrocatalyst. The fine nanoparticles and high activity enable significant (∼60 %) reduction in the Ir metal loading required to obtain equivalent OER performance. In addition, when evaluated through an accelerated stress test using potential cycling, the catalyst exhibits outstanding durability (79 % retention) compared to that of the commercial equivalent (66 % retention). The OER activity loss was attributed to the catalyst dissolution (30 % loss) and the catalyst particle growth (70 %), with no measurable loss due to the TiN support corrosion. The development of ultra‐fine IrO2@Ir nanoparticles and robust ceramic catalyst support significantly improved the Ir utilization and open a new perspective for supported OER catalyst.
Modeling and optimization of malondialdehyde (MDA) absorbance behavior through response surface methodology (RSM) and artificial intelligence network (AIN): An endeavor to estimate lipid peroxidation by determination of MDA
Authors: Akbari Behnaz , Najafi Farhood , Bahmaei Manochehr , Mahmoodi Niyaz Mohammad , Sherman Janet Hope 
Published: January 2023

AbstractOxidative stress (OS) associated with reactive oxygen species (ROS) attacks many biomolecules, leading to cell death, lipid peroxidation (LP), and physiological mechanism damage in the human body because of its reaction with nucleotides, membrane lipids, and proteins. Malondialdehyde (MDA) is one of the end products of polyunsaturated fatty acids peroxidation. The elevated level of MDA is widely known as a biomarker for the indirect measurement of OS during LP. Although several derivatizations' approaches and successful commercial kits are available, their analytical validity and reliability in clinical studies require further attention to obtain robust quantitation and high‐quality data. Also, re‐evaluation and development of new analytical methods with high sensitivity and selectivity in response to free MDA and total MDA, DNA and protein adducts are not well‐characterized. Here, response surface methodology (RSM) and artificial neural network (ANN) were proposed to model, predict, and optimize MDA detection. This paper introduced a novel, simple, and fast modeling method using a new reagent (para methoxy aniline or PMA) for the first time to convert MDA to an adduct which could be detectable by UV‐Vis spectroscopy. Based on the interactions between MDA and PMA at times and temperatures, RSM and artificial intelligence network (AIN) were then applied to forecast the absorbance rate of MDA‐PMA. The optimum mode for the highest absorbance rate of MDA‐PMA is at the temperature of 74.99°C with a PMA concentration of 499.87 μM and MDA concentration of 49.98 μM. The best structure with five hidden layers, including 5,5,5,9,4 neurons with the transfer function logsig for each layer, was selected for the MLP‐ANN model. The maximum error rate of the MLP‐ANN model was 2.08%.Our new approach is an improvement over existing assay kits, overcoming limitations such as time, temperature, and reliability with a bright future to target increased MDA level in human samples.
A Semiconductor Biohybrid System for Photo‐Synergetic Enhancement of Biological Hydrogen Production
Authors: Yi Ziqian , Tian Shouqin , Geng Wei , Zhang Tongkai , Zhang Wen , Huang Yaoqi , Barad Hannah‐Noa , Tian Ge , Yang Xiao‐Yu 
Published: January 2023

AbstractCdS nanoparticles were introduced on E. coli cells to construct a hydrogen generating biohybrid system via the biointerface of tannic acid‐Fe complex. This hybrid system promotes good biological activity in a high salinity environment. Under light illumination, the as‐synthesized biohybrid system achieves a 32.44 % enhancement of hydrogen production in seawater through a synergistic effect.
Live Monitoring of Anionic Living Polymerizations by Electrospray‐Ionization Mass Spectrometry
Authors: Eisele Niklas F. , Peters Matthias , Koszinowski Konrad 
Published: January 2023

AbstractAnionic polymerizations are of exceptional practical importance, but difficult to analyze due to the high reactivity of the growing polymer chains. Here, we demonstrate that electrospray‐ionization mass spectrometry (ESI‐MS) permits direct observation of the active carbanionic intermediates formed in the anionic ring‐opening polymerization of 1‐cyanocyclopropanecarboxylate in tetrahydrofuran. This includes the identification of a side product, as well as real‐time analysis of the polymerization reaction. From the mass spectra obtained, we can derive not only the mean molar mass and the polydispersity, but also the rate constants for the initiation and the individual propagation steps. The initiation proceeds significantly faster than the propagation steps. Accordingly, the examined reaction corresponds to a living polymerization, as we also confirmed by additional control experiments. Besides giving detailed insight into the reaction system probed here, we also expect the presented methodology to make possible the in‐situ analysis of further anionic polymerizations.
Total Turnover Number – a Key Criterion for Process Evaluation
Authors: Bommarius Andreas S. 
Published: January 2023

AbstractThe dimensionless total turnover number TTN, the average number of turnovers per active site of a catalyst over the catalyst's lifetime, is a universal criterion for the operational stability of a catalyst. If the cost of the catalyst is known, the cost contribution per catalytic cycle can be determined. The present work honors the contributions by Prof. Christian Wandrey and his group on the topic of TTN and describes some recent developments on the subject.
CD47 and CD68 expression in breast cancer is associated with tumor‐infiltrating lymphocytes, blood vessel invasion, detection mode, and prognosis
Authors: Chen Ying , Klingen Tor Audun , Aas Hans , Wik Elisabeth , Akslen Lars A 
Published: January 2023

AbstractCD47 expressed on tumor cells binds to signal regulatory protein alpha on macrophages, initiating inhibition of phagocytosis. We investigated the relationships between tumor expression of CD47 and CD68 macrophage content, subsets of tumor‐infiltrating lymphocytes (TILs), and vascular invasion in breast cancer. A population‐based series of 282 cases (200 screen detected and 82 interval patients) from the Norwegian Breast Cancer Screening Program was examined. Immunohistochemical staining for CD47 and CD68 was evaluated on tissue microarray (TMA) slides. For CD47 evaluation, a staining index was used. CD68 tumor‐associated macrophages were counted and dichotomized. TIL subsets (CD45, CD3, CD4, CD8, and FOXP3) were counted and dichotomized using immunohistochemistry on TMA slides. Vascular invasion (both lymphatic and blood vessel) was determined on whole tissue slides. High CD47 tumor cell expression or high counts of CD68 macrophages were significantly associated with elevated levels of all TIL subsets (p < 0.02), CD163 macrophages (p < 0.001), blood vessel invasion (CD31 positive) (p < 0.01), and high tumor cell Ki67 (p < 0.004). High CD47 expression was associated with ER negativity (p < 0.001), HER2 positive status (p = 0.03), and interval‐detected tumors (p = 0.03). Combined high expression of CD47–CD68 was associated with a shorter recurrence‐free survival (RFS) by multivariate analysis (hazard ratio [HR]: 2.37, p = 0.018), adjusting for tumor diameter, histologic grade, lymph node status, and molecular subtype. Patients with luminal A tumors showed a shorter RFS for CD47–CD68 high cases by multivariate assessment (HR: 5.73, p = 0.004). This study demonstrates an association of concurrent high CD47 tumor cell expression and high CD68 macrophage counts with various TIL subsets, blood vessel invasion (CD31 positive), other aggressive tumor features, and interval‐presenting breast cancer. Our findings suggest a link between CD47, tumor immune response, and blood vessel invasion (CD31 positive). Combined high expression of CD47–CD68 was an independent prognostic factor associated with poor prognosis in all cases, as well as in the luminal A category.
Polymeric Janus Fibers
Authors: Lamberger Zan , Zainuddin Shakir , Scheibel Thomas , Lang Gregor 
Published: January 2023

AbstractJanus fibers are a class of composite materials comprising mechanical and chemical to biological functionality. Combining different materials and functionalities in one micro‐ or even nanoscale fiber enables otherwise unreachable synergistic physicochemical effects with unprecedented opportunities for technical or biomedical applications. Here, recent developments of processing technologies and applications of polymeric Janus fibers will be reviewed. Various examples in the fields of textiles, catalysis, sensors as well as medical applications, like drug delivery systems, tissue engineering and antimicrobial materials, are presented to illuminate the outstanding potential of such high‐end functional materials for novel applications in the upcoming future.