bluuebunny/crossref_metadata_2025 huggingface dataset:
Designing a Simple Quinoline‐Based Chromo‐Fluorogenic Receptor for Highly Specific Quantification of Copper (II) Ions: Environmental and Bioimaging Applications
Authors: Durgaparameshwari Murugavel , Kaviya Karuppaiyan , Prabakaran D. S. , Santhamoorthy Madhappan , Rajamanikandan Ramar , Al‐Ansari Mysoon M. , Mani Kailasam Saravana
Published: December 2024

Many industries use copper metal ions (Cu2+ ions), and their salts are utilized as supplemental materials in both agriculture and medicine. Identifying and monitoring these Cu2+ ions in biological and environmental specimens is crucial due to their association with several health issues. In this investigation, we have designed a simple quinoline‐based receptor (E)‐3‐(((2,4‐di‐tert‐butyl‐5‐hydroxyphenyl)imino)methyl)‐6‐methoxyquinolin‐2(1H)‐one (QAP) containing imine functional groups to inspect its capability to identify metal ions in a semi‐aqueous medium. The photophysical characteristics and structural confirmation of the receptor QAP were investigated using various spectroscopic techniques. Among various metal ions, the receptor QAP displayed an intense color shift from slightly yellow to strong yellow in the existence of Cu2+ ions, as visualized by the nude eye. Furthermore, the fluorescence spectral maximum wavelength at 485 nm and the strong cyan fluorescence color were quenched upon introducing Cu2+ ions. The alteration in the spectral and colorimetric features of QAP with Cu2+ ions is due to coordination complex formation. The present sensor shows the linear range from 3 to 69 μM, subsequent in a computed limit of detection as 3.16 nM, which is much lower than that of the maximum threshold of Cu2+ ions in drinking water set by WHO. Therefore, the receptor can respond to Cu2+ ions sensing in two ways: by changing color and by quenching fluorescence. The binding mode of the Cu2+ ions to the functional groups of the receptor QAP is a 1:1 stoichiometry, according to ESI‐mass, Job's plot analysis, and density functional theory (DFT) computations. The practical utility of the fluorescent receptor QAP was applied for Cu2+ ions determination in environmental samples (drinking, tap, and dam water) and cancer cells (HeLa cells).
Fluorescent Staining–Assisted Evaluation of the Anticancer Potential of Nyctanthes arbor‐tristis Extracts in HepG2 Liver Cancer Cells
Authors: Murali Jeeva , Rajendran Venkatesh , Balasubramanian Venkatrajah , Sampath Shobana , AlSalhi Mohamad S. , Devanesan Sandhanasamy
Published: December 2024

The current study's initial goal was to investigate the anticancer activity of the extracts from the flowering plant Nyctanthes arbor‐tristis. The ethanol extracts' phytochemical analysis was qualitatively determined. It was determined that the various phytochemical substances had antibacterial, antioxidant, and anticancer effects. GC‐MS analysis revealed compounds like maleic anhydride, butanedioic acid, and oxalic acid emphasize the antioxidant and anticancer properties. MTT assay was investigated against three different cell lines (HepG2, A549, and MCF7). High level of resistance to HepG2 liver cancer cell lines was noted with ethanol flower extracts with IC50 value of 67.98 μg/mL. EtBr staining assay revealed HepG2 apoptotic cells displaying nuclear and membrane alterations when exposed to 70 μg/mL of ethanol extract. The cells treated with 70 μg/mL of extract showed a reduction of mitochondrial membrane potential, as evidenced by the MMP assay, which showed red fluorescence decreasing and green fluorescence increasing. DNA fragmentation analysis showed HepG2 cancer cells showed no signs of DNA fragmentation after being treated with 50 μM treatments of flower extracts for 72 h. Quantitative RT‐PCR analysis showed increased Bcl2 gene expression with fold variation level of about 0.086094579. The obtained results emphasized the significance of Nyctanthes arbor‐tristis extracts with a suggestion of chemotherapeutic medication to treat various cancers in the future.
GOLPH3‐STIP1 Complex Activates STAT3 Through Exosome Secretion to Induce Colon Cancer Metastasis
Authors: Guo Yanta , Hong Zhongshi , Huang Sifu , Wu Yuze , Qiu Chengzhi , Xu Jianhua
Published: December 2024

With a high mortality rate, colon cancer (CC) is the third most common malignant tumor worldwide. The primary causes are thought to be the high invasiveness and migration of CC cells. The functions of Golgi phosphoprotein 3 (GOLPH3), stress‐induced phosphoprotein 1 (STIP1), and the signal transducer and activator of transcription 3 (STAT3) signaling pathway in the invasion and migration of CC cells were examined in this study. We collected the exosomes by high‐speed centrifugation. The expressions of GOLPH3, STIP1, and epithelial‐mesenchymal transition (EMT)‐related proteins in CC tissues, cells, and exosomes were analyzed using Western blotting (WB) experiments. The abilities of CC cell invasion and migration were evaluated by the Transwell assay. The binding relationship between GOLPH3 and STIP1 was validated through Co‐immunoprecipitation (Co‐IP), and their sublocalization in CC cells was determined by immunofluorescence detection under laser confocal microscopy. Immunohistochemistry (IHC) experiments detected the expression levels of each protein in the transplanted tumor mass. Animal experiments confirmed the impact of the GOLPH3/STIP1/STAT3 regulatory axis on CC growth. We found that in CC tissues and cells, GOLPH3 was highly expressed, and silencing GOLPH3 not only greatly reduced CC cell invasion and migration but also prevented EMT. Furthermore, GOLPH3 and STIP1 interacted in CC cells, and the GOLPH3‐STIP1 complex affected the capacity for cell invasion and migration by triggering the STAT3 signaling pathway. Noteworthily, GOLPH3, and STIP1 could also be detected in CC cell exosomes, and the exosomes carried the GOLPH3‐ST1P1 complex to act on CC cells to activate intracellular STAT3 signaling, ultimately affecting the cancer cell migration and invasion. The above molecular regulatory mechanisms have also been validated in mice. In conclusion, the GOLPH3‐STIP1 complex acted on surrounding CC cells through exosomes and activated the STAT3 signaling pathway to stimulate CC cell invasion and migration.
Seasonal Variations in Triptan Prescription in Japan: A Nationwide Time‐Series Analysis
Authors: Tatsumoto Muneto , Hirata Koichi , Nakayama Takeo , Yamato Kentaro , Sano Hiromi , Inuyama Lyo
Published: December 2024

Objective

This study aimed to investigate seasonal differences in migraine onset in Japan and associated trends in the prescription of triptan.

Background

The relationship between seasonal changes and the onset of migraine remains largely unknown.

Methods

We combined the large‐scale medical claims data in Japan with city‐level meteorological data presented by the Japan Weather Association. The study period was from January 2018 to December 2019. We included patients aged 18–74 years and diagnosed with migraine who had been prescribed triptans in 2018. Patients were categorized into four groups according to the seasons when they were prescribed medicines: winter (January–March), spring (April–June), summer (July–September), and autumn (October–December). Migraine onsets were defined by the time of triptan prescription. The least‐square mean differences between the seasons were estimated with linear mixed‐effects models for repeated measures, adjusting for the following covariates: sex, age, acute migraine medications, and medications for migraine prevention, comorbidities that can induce migraine, other comorbidities, and the estimated age of menopause in females.

Results

We analyzed data of 12,986 patients in 2019 after triptan had been prescribed (female 74.1%). The mean age was 44.1 years. The mean number of amounts of prescriptions comprised 2.12 tablets/month in spring and summer, whereas there were only 2.09 tablets/month in autumn and 2.00 tablets/month in winter. The amount of triptan prescribed in winter was lower than in spring (β = −0.117; 95% confidence interval [CI]: −0.169 to −0.065).

Conclusion

The study results suggest that seasons can have an impact on the onset of migraine; thus, clinicians may advise patients to take preventive actions, including self‐care and drug therapies, from the winter stage. This should be done in order to reduce the number of migraine onsets in high‐risk season (spring) regardless of region.
Reliability and Validity of the Turkish Version of the Acute Stroke Management Questionnaire
Authors: Adadıoğlu Öznur , Acar Bilgehan Atılgan , Acar Türkan
Published: December 2024

Objective

The current research was carried out to test the validity and reliability of the Turkish version of the Acute Stroke Management Questionnaire (ASMaQ), developed to determine the acute stroke management awareness of health‐care professionals.

Methods

This methodological study was performed in a training and research hospital. Data were collected using the “Participant Interview Form” and the Acute Stroke Management Questionnaire.

Results

The Content Validity Index (CVI) of the Acute Stroke Management Questionnaire was found to be 0.91. As a result of exploratory factor analysis (EFA), it was revealed that the scale, which was adapted to Turkish, consisted of 3‐factor and 29 items, as in its original form. Confirmatory factor analysis confirmed the 3‐factor structure of the scale. The ASMaQ exhibited strong internal consistency (Cronbach's alpha 0.96) and test–retest reliability (0.879).

Conclusion

The 29‐item and three‐dimensional structure of the Acute Stroke Management Questionnaire was revealed to be a valid and reliable measurement tool that could be utilized in evaluating the acute stroke management awareness of health‐care professionals in the Turkish language and culture.
Community Participation in Native American and White Individuals After Traumatic Brain Injury: A 5‐Year Longitudinal Model Systems Study
Authors: Watson Jack D. , Perrin Paul B. , Xia Bridget , Arango‐Lasprilla Juan Carlos
Published: December 2024

Purpose/Objective

This study examined (a) differences in demographic and injury‐related characteristics following traumatic brain injury (TBI) between Native American and White individuals; (b) differences in community participation between Native American and White individuals with TBI at 1, 2, and 5 years after TBI; and (c) whether demographic or injury‐related characteristics account for community participation disparities.

Research Method/Design

A sample of 63 Native American individuals demographically matched to 63 White individuals (n = 126) was enrolled while on acute rehabilitation for moderate or severe TBI. Baseline demographic and injury‐related characteristics were collected at this time and the Participation Assessment with Recombined Tools (PART‐O) measure of community participation at 1, 2, and 5 years after TBI.

Results

Native American individuals were less likely to have private insurance and be employed at the time of injury and more likely to have had lower educational attainment and engaged in binge drinking in the month prior to TBI compared to White individuals. Native American individuals demonstrated lower Out and About scores but statistically equivalent Social and Productivity scores. The difference in Out and About scores did not change as a function of time, and the overall difference between the two groups dissipated with the inclusion of statistically different sociodemographic variables.

Conclusions/Implications

Clinicians can provide culturally sensitive, patient‐ and family‐centered care by conducting comprehensive interviews and identifying strengths as well as risk factors that enhance or hinder community participation after TBI in Native American individuals.
A Randomized Controlled Trial of Mindfulness Meditation Combined With BrainLink Intelligent Biofeedback Instrument on Pancreatic Cancer Patients Under Chemotherapy
Authors: Mi Na , Zhang Shu‐Ting , Sun Xiao‐Li , Li Ting , Liao Yu , Dong Lei , Chu Ling‐Ling
Published: December 2024

Background

Adjuvant chemotherapy can promote the 5‐year overall survival rate of pancreatic cancer (PC) patients to 16%–21%. However, the negative emotions of patients, such as anxiety, are usually omitted. Moreover, their disease burden concentrates on pain symptoms, seriously affecting the quality of life of patients. How to improve the negative emotions of PC patients, alleviate their pain, and ameliorate their quality of life has become an urgent issue.

Objective:

To explore the effect of mindfulness meditation (MM) combined with the BrainLink intelligent biofeedback instrument on the anxiety, pain, brain fatigue, and quality of life of PC patients under chemotherapy.

Method:

A total of 145 PC patients under chemotherapy were admitted to the Department of Hepatobiliary Surgery of the Second Affiliated Hospital of Army Military Medical University from January 2022 to March 2024 and were incorporated as study objects. They were divided into a control group (n = 72) and a test group (n = 73) according to the random number table. The control group received routine nursing treatment; the experimental group was treated with MM combined with an intelligent biofeedback instrument. The general information, anxiety (SAS), pain (VAS), EEG signal data (degrees of fatigue, concentration, and relaxation and EEG waves), and quality of life (EORTC QLQ‐C30) of the two groups before intervention and 4th, 8th, and 12th weeks after intervention were compared.

Result

There is no significant difference in baseline data and pathological features between the two groups. After the 4th, 8th, and 12th weeks of intervention, the SAS values of the experimental group are remarkably lower than those of the control group (p < 0.05). In the 4th, 8th, and 12th weeks of intervention, the VAS scores of the experimental group are apparently lower than those of the control group (p < 0.05). In the 4th, 8th, and 12th weeks of intervention, the score of the quality of life (EORTC QLQ‐C30) in the experimental group is significantly higher than that in the control group (p < 0.05). In the 4th, 8th, and 12th weeks, compared with the control group, the experimental group patients showed significant improvement in brain fatigue relief, concentration, and relaxation levels (p < 0.05), while the experimental group's brain α and θ. The wave showed an upward trend (p < 0.05).

Conclusion

MM combined with the BrainLink intelligent biofeedback instrument can significantly mitigate the anxiety, pain severity, and brain fatigue relief degree of PC patients under chemotherapy, thereby promoting their quality of life. It provides a novel intervention for the psychosomatic health of PC patients under chemotherapy.
The Antagonism Hypothesis: A New View on the Emergence of Consciousness
Authors: Xiong Weirui , Yu Lu
Published: December 2024

Purpose

The generation of consciousness poses a complex scientific challenge. Neuroscience and biological sciences have extensively studied this phenomenon, yielding numerous theories and hypotheses. However, to date, no reliable evidence has emerged to exclude any hypothesis conclusively, nor has any theory garnered unanimous agreement. This study aims to offer novel insights for further in‐depth study on consciousness.

Method

A new theoretical hypothesis was proposed based on reviews and comments from predictive processing theory, information theory, thermodynamics, and neuroscience.

Findings

This study argues that, first, it is necessary to clarify that the core implication of the concept of consciousness is first‐person perception. Accordingly, the study of consciousness is based on this premise. Second, on this basis, the antagonistic hypothesis of consciousness generation was proposed. This hypothesis holds that consciousness arises from the antagonism of mature individual experiences that cannot be seamlessly integrated with the function of addressing and navigating these conflicts.

Conclusion

The antagonism hypothesis is a new concept regarding the generation of consciousness that deserves further study.
IGF2BP2 Shapes the Tumor Microenvironment by Regulating Monocyte and Macrophage Recruitment in Bladder Cancer
Authors: Li Jianpeng , Jiang Yunzhong , Ma Minghai , Wang Lu , Jing Minxuan , Yang Zezhong , Wang Lizhao , Qiu Quanpeng , Song Rundong , Pu Yuanchun , Zhang Yuanquan , Mei Nan , Zhang Mengzhao , Fan Jinhai
Published: December 2024

Background

Immunotherapy has shown promise for bladder cancer (BC) treatment but is effective only in a subset of patients. Understanding the tumor microenvironment (TME) and its regulators, such as the expression of N6‐methyladenosine (m6A) regulators, may improve therapeutic outcomes. This study focuses on the role of IGF2BP2, an m6A reader, in modulating the BC TME.

Methods

Transcriptomic and single‐cell RNA‐seq data from public databases were analyzed to identify BC subgroups and investigate IGF2BP2's role in the TME. Clustering and PCA identified key m6A regulators. NicheNet and SCENIC analyses were used to predict cell–cell interactions and transcriptional regulators, respectively. IGF2BP2's role in macrophage recruitment was validated via co‐culture experiments and RNA sequencing.

Results

Unsupervised clustering identified BC subgroups with distinct TME characteristics, with IGF2BP2 emerging as a key regulator associated with poor prognosis and reduced response to immunotherapy. Single‐cell analysis revealed IGF2BP2's high expression in the GE‐9 epithelial subpopulation, characterized by immune evasion features and cytokine‐mediated macrophage recruitment. NicheNet analysis showed that GE‐9 cells interact with monocyte/macrophage populations through cytokine signaling. Co‐culture experiments confirmed IGF2BP2's role in recruiting macrophages, partially mediated by CCL2. Furthermore, IGF2BP2 expression was linked to immunosuppressive M2‐like and SPP1+ macrophages, contributing to an angiogenesis‐promoting and immunosuppressive TME.

Conclusion

IGF2BP2 shapes the BC TME by modulating macrophage infiltration and polarization, leading to an immunosuppressive microenvironment that hinders immunotherapy. Targeting IGF2BP2 could enhance the efficacy of current therapies and improve patient outcomes.
Mutational Landscape of Bone Marrow CD19 and CD138 Cells in Waldenström Macroglobulinemia (WM) and IgM Monoclonal Gammopathy of Undetermined Significance (IgM MGUS)
Authors: Trojani Alessandra , Beghini Alessandro , Bossi Luca Emanuele , Stefanucci Marta Rachele , Palumbo Cassandra , Greco Antonino , Frustaci Annamaria , Di Camillo Barbara , Cairoli Roberto
Published: December 2024

Background

Despite recurrent and activating mutations, including MYD88, CXCR4, ARID1A, KMT2D, and CD79B were identified, the genetic basis for Waldenström's Macroglobulinemia (WM) and the risk of progression of IgM MGUS to WM remain to be fully elucidated.

Methods

We investigated the mutation status of WM (n = 8), sWM (n = 7), and IgM MGUS (n = 5) patients, by performing high‐throughput targeted AmpliSeq NGS on 117 target genes. Specifically, we analyzed the CD19+ cells from 15 WM/sWM patients and five IgM MGUS patients. We also analyzed the CD138+ cells from four WM/sWM patients and two IgM MGUS patients.

Results

We detected the classic mutation MYD88L265P in 93% of WM/sWM and in 60% of IgM MGUS patients. The CXCR4S338Ter mutation was identified in 26% of WM/sWM patients, whereas it was undetectable in IgM MGUS subjects. Interestingly, we identified new mutated genes, including WNK2 somatic mutations affecting 46% of WM/sWM patients, for which a recurrent allelic variant (V1635Ter) was observed in this cohort. Moreover, sequencing evaluation revealed recurrently frameshift or missense mutations involving NFKB2 (L473Afs) in 60% of IgM MGUS and 20% of WM/sWM, PTPN13 (P1546Tfs) in 20% of IgM MGUS and 7% of WM/sWM, CARD11 (S622del) in 20% of IgM MGUS and 20% of WM/sWM, KMT2C (I823T) in all IgM MGUS and 93% of WM/sWM, and ATM in 20% of IgM MGUS and 47% of WM/sWM patients.

Conclusion

In conclusion, we uncovered new insights into the mutational landscape of WM, depicting a more complex involvement of the NF‐kB pathway, and providing evidence of the recurrence of some variants (MYD88, IL17RB, NFKB2, ATM, CARD11, PTPN13, and WNK2) also in IgM MGUS.
Novel Approaches in Targeting Cell Surface and Secreted Proteins for Lysosomal Degradation
Authors: Eldeeb Mohamed A. , Hohman Grace , Shahid Michael
Published: December 2024

Protein degradation is pivotal for all biochemical aspects of cellular function. In mammalian cells, protein degradation is mediated mainly by the ubiquitin proteasome system (UPS) and the autophagic‐lysosomal system (ALS). Over the last two decades, different types of targeted protein degradation approaches have been developed including proteolysis targeting chimeras (PROTACs) and lysosome targeting chimeras (LYTACs), which employ the UPS to degrade intracellular proteins and the ALS to degrade extracellular and membrane proteins respectively. Nevertheless, Current targeted membrane protein degradation approaches face some inherent challenges including limited target protein degradation efficacy and cell type specific applicability. Herein, we highlight some recent developments of novel targeted membrane protein degradation modalities that exhibit wide‐applicability and high protein degradation efficiency. These novel membrane protein degraders hold tremendous promise as new pharmacological and biochemical tools in targeting membrane and secretory proteins for lysosomal degradation.
Ruthenium‐Doped Copper Nanowires for Nitrite/Nitrate to Ammonia Conversion and Their Integration in Zinc–Nitrite Batteries
Authors: Rios‐Studer Tobias , Chen Zhengfan , Nickel Christean , Feng Fan , Sowa Kevin , Oseghe Ekemena O. , Akbari Sina Sadigh , Rahali Sarra , Prädel Leon , Lieberwirth Ingo , Zhang Guangjin , Gao Dandan , Liu Rongji , Streb Carsten
Published: December 2024

The electrochemical reduction of nitrite (NO2−) and nitrate (NO3−) not only enables sustainable, circular routes to produce ammonia (NH3), but also eliminates pollutants in groundwater. In this article, we report a facile synthesis of Ru‐doped Cu nanowires on Cu foam electrodes with low Ru (0.48 wt.%) loading. The composite electrode shows high‐performance in the NO2−/NO3− to NH3 electroreduction, giving NH3 Faradaic efficiency of up to 100% and NH3 yield rates up to 33.2 mg h−1 cm−2 at −0.2 V versus RHE in NO2− reduction. For the nitrate‐to‐ammonia reduction, the electrode also shows high activity with Faradaic efficiency of 88.4% (at −0.6 V versus RHE) and a yield rate of 62.5 mg h−1 cm−2 (at −1.0 V versus RHE). We show that the electrode can easily be integrated into a Zn–nitrite battery, giving a power density of 9.1 mW cm−2, a NH3 yield rate of 1.88 mg h−1 cm−2 and a nitrite‐to‐ammonia Faradaic efficiency of 88.9% at a current density of 20 mA cm−2. The system combines three productive outputs, that is removal of NOx− pollutants, synthesis of valuable NH3 and generation of “green” electricity.
Biocatalytic Reductive Amination for In Vitro Biosynthesis of the Amaryllidaceae Alkaloid Precursor
Authors: Zhang Yuhao , Huang Shuhui , Liu Wan‐Qiu , Li Jian
Published: December 2024

Amaryllidaceae alkaloids (AAs) are plant‐derived natural compounds with diverse bioactivities. To biosynthesize AAs, 4′‐O‐methylnorbelladine (4′‐MB) is a key precursor that is first formed by C–N coupling between tyramine and 3,4‐dihydroxybenzaldehyde catalyzed by a NADPH‐dependent reductase. However, 3,4‐dihydroxybenzaldehyde is oxygen sensitive and not stable due to its catechol moiety when constructing an in vitro enzymatic system for 4′‐MB synthesis. To address this issue, we design an artificial biosynthetic route to synthesize 4′‐MB. First, we choose isovanillin instead of 3,4‐dihydroxybenzaldehyde as an alternative substrate. Then, a short‐chain dehydrogenase/reductase (SDR) from Zephyranthes treatiae is utilized to couple tyramine and isovanillin. After demonstrating the synthesis of 4′‐MB, we optimize the whole biocatalytic system with enhanced performance. The final enzymatic system can be reused for multiple cycles with the help of a crystalline inclusion protein (CipB)‐mediated enzyme immobilization. Additionally, we scale up the reaction system from 50 µL to 10 mL, generating approximately 800 µM of 4′‐MB. We envision that our work will provide an efficient and sustainable approach to produce 4′‐MB, which could support the large‐scale production of Amaryllidaceae plant‐originated natural products.
Hybrid Inclusion Materials Based on Chiral Nematic Mesoporous Organosilica with Incorporated Cyclodextrin Receptors
Authors: Szymkowiak Joanna K.
Published: December 2024

The creation of multicomponent materials with desired properties and functions is a challenge of modern materials chemistry. Chiral nematic mesoporous organosilicas have iridescent properties that make them attractive for decoration and sensing. In this paper, we demonstrate the chemical functionalization of chiral nematic mesoporous organosilica films with cyclodextrin. In this way, we have been able to create chiral nematic mesoporous films with macrocyclic molecules on the surface to obtain a new class of hybrid inclusion materials.
Microwave‐Assisted Synthesis of Platinum‐free High‐Entropy Alloy Catalysts on Reduced Graphene Oxide Sheets for Enhanced Oxygen Reduction and Evolution Reactions
Authors: Bib Khan Jala , Kumar Panda Pradeep , Dash Pranjyan , Hsieh Chien‐Te
Published: December 2024

Nano‐sized high‐entropy materials (HEMs) recently received more attention to researchers due to their superior electrochemical catalytic properties. HEMs comprise at least five elements with or without metals and are synthesized through solid‐state reactions and solution‐mediated techniques. The presence of many elements in these HEMs result in a high mixing entropy and facilitates the formation of stable solid solutions in fundamental crystal structures. Herein, Pt‐free high‐entropy alloys (HEAs) were synthesized through facile and straightforward pulse microwave (PM) synthesis technique, which serve as efficient electrochemical catalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). The PM synthesis method was conducted at an extremely low temperature (100 °C) without any external catalytic reagents. Using this PM technique, Cr18.2Zr13.5Ti5.3Co17.8Ni8.4Cu8.5Fe28.3 and Al15.3Mn18.2Ti3.7Co23.2Ni5.9Cu5.9Fe27.8 HEAs catalysts were synthesized with superior catalytic activity towards OER and ORR and compare its activities with pure Pt catalysts. The as‐prepared HEAs also display an anti‐CO poisoning effect and long‐term durability, as compared to pure Pt catalysts. The low‐temperature PM approach not only confirms the feasibility of synthesis of noble metal‐free HEAs but also validates their superior catalytic activity towards OER and ORR, which is beneficial for the development of proton exchange membrane fuel cells and proton exchange membrane water electrolysis.
Biomimetic Pseudopeptides to Decipher the Interplay between Cu and Methionine‐Rich Domains in Proteins
Authors: Badillo‐Gómez Joel I. , Suarez‐Antuña Irene , Mazurenko Ievgen , Biaso Frédéric , Pécaut Jacques , Lojou Elisabeth , Delangle Pascale , Hostachy Sarah
Published: December 2024

Maintaining tightly copper homeostasis is crucial for the survival of all living organisms, in particular microorganisms like bacteria. They have evolved a number of proteins to capture, transport and deliver Cu(I), while avoiding Fenton‐like reactions. Some Cu proteins exhibit methionine‐rich (Met‐rich) domains, whose role remains elusive. In this work, we designed biomimetic compounds recapitulating the possible Cu(I) binding sites in these domains, in order to examine the parameters important for Cu(I) binding. Five different biomimetic pseudopeptides were synthesized, exhibiting either three methionines or two methionines and a third amino acid likely to be present in the Met‐rich domain. The affinities for Cu(I) of these model binding sites were determined, as well as their redox properties and behavior in the presence of Cu(II). Our results highlight the importance of Met residues, and their abundance in Met‐rich domains, to efficiently bind Cu(I) in the periplasmic space.
Reductive Zincke Reaction: Opening of Pyridinium Rings to δ‐Amino Ketones via Transfer Hydrogenation
Authors: Qi Leiming , Chen Zhenyu , Aïssa Christophe , Xiao Jianliang
Published: December 2024

The Zincke reaction and Birch reduction have been one of the few reactions that allow for ring opening of pyridines ever since the discovery of pyridine more than a century ago. This paper presents a new addition to the list of pyridine ring‐opening reactions, reductive Zincke reaction, which affords saturated δ‐amino ketones. Under the catalysis of a simple rhodium complex, pyridinium salts with diverse substituents are reduced with formic acid, ring‐opened with water, transaminated with a secondary amine and further reduced to afford a wide range of δ‐amino ketones, including those in which the alkane chain of the ketones is selectively deuterated or fluorinated. The applicability of the reaction is exemplified by the synthesis of drug analogues and late‐stage modification of drug molecules.
Kinetic Modelling and Machine Learning Approaches on the Conductance Transients of Zn0.5Ni0.5Fe2O4 Sensors for Addressing Cross‐sensitivity towards Ethanol and Acetone Vapors
Authors: Bhagat B. , Paine S. , Manna B. , Choudhury A. , Mukherjee K.
Published: December 2024

The accurate discrimination among various volatile organic compounds, especially ethanol and acetone possess a serious concern for metal oxide based chemiresistive sensors. The work presents a systematic approach to address the issue by utilizing superior sensing potentiality of Zn0.5Ni0.5Fe2O4 coupled with efficient machine learning (ML) techniques. The work provides a thorough understanding on the synthesis, characterization of Zn0.5Ni0.5Fe2O4 nanoparticles and evaluates their sensing performance towards ethanol and acetone vapors. The optimized sensor performance recorded under varying concentrations (100–1000 ppm) of analytes across the range of temperature (225–300 °C) provides lesser selectivity between acetone and ethanol. The Langmuir‐Hinshelwood reaction mechanism was invoked further to address the selectivity issue by modelling the response transients of the sensor to get an insight into sensing interaction at a microscopic level. The estimated activation energy values of ethanol (0.26 eV) have been found to be smaller compared to that of acetone (0.34 eV), explaining little higher response of the sensor towards ethanol. Moreover, some efficient ML algorithms were employed to predictively analyze the acquired sensing data for achieving more precise discriminations between these two analytes.
Photoexcited Hantzsch Ester Anions Enabled C−F Bond Activation and Hydro‐Difluoroalkylation of Arylethylenes Through Dual‐SET Process
Authors: Li Nan , Si Jia‐Le , Xu Meng‐Yu
Published: December 2024

In this study, we reported a new approach to activate the C−F bond of trifluoromethylarenes to achieve the hydro‐difluoroalkylation of arylethylenes using photoexcited Hantzsch esters (HEs) anions. A wide range of α,α‐difluoroalkanes was synthesized. Late‐stage functionalization of drug molecules and synthesis of bioactive molecule bioisostere were also presented. Mechanistic studies revealed that the dual‐single electron transfer (SET) process of HEs anion was the key to this reaction.
Synthesis and Properties of Symmetrical and Asymmetrical Polyferrocenylmethylenes
Authors: Feuerstein Aylin , Rittner Till , Boßmann Blandine , Gießelmann Elias C. J. , Schu Justin , Morgenstern Bernd , Gallei Markus , Schäfer André
Published: December 2024

The synthesis of differently substituted polyferrocenylmethylenes (PFM) via ring‐opening transmetalation polymerization (ROTP) is reported. A number of novel, symmetrically and asymmetrically substituted carba[1]magnesocenophanes have been prepared, which were used as precursors and allowed investigations of the influence of different substitution patterns on the PFM polymer properties. The novel carba[1]magnesocenophanes have been fully characterized by 1H and 13C{1H} NMR spectroscopy, and structurally authenticated by single‐crystal X‐ray diffraction (SC‐XRD). The corresponding PFMs were obtained with molecular weights in a range of Mw=1900 g mol−1 up to 15100 g mol−1 and corresponding dispersities of Đ=1.48 to 1.81. All PFMs have been fully characterized by 1H and 13C{1H} NMR spectroscopy, as well as by gel permeation chromatography (GPC), thermal gravimetric analysis (TGA) and matrix assisted laser desorption ionization‐time‐of‐flight (MALDI‐ToF) mass spectrometry. Pyrolysis of spyrocyclic substituted PFM resulted in a ceramic yield above 50 %, while the obtained residue was characterized by powder X‐ray diffraction (PXRD).
Interfacial Synergism in NiMoO4/FeOOH Heterostructure for Enhanced Alkaline Oxygen Evolution and Urea Oxidation
Authors: Chen Junyi , Wang Jing , Lou Dongsheng , Xiang Yingying , Sun Tongming , Tang Yanfeng , Wang Minmin
Published: December 2024

FeOOH with excellent catalytic properties for oxygen evolution and also considered to be a true active site has attracted great interest in recent years. However, the intrinsic low conductivity limits its catalytic performance. Herein, a one‐dimensional core‐shell NiMoO4/FeOOH heterojunction with high OER activity and stability was developed. At current densities of 10 and 100 mA cm−2, low overpotentials of 194 and 266 mV are need to drive oxygen evolution, meanwhile, the electrode exhibits high catalytic kinetics with small Tafel slopes of 53.4 mV dec−1 and excellent stability over 100 hours. Further analysis showed that the ultrathin FeOOH layer (~5 nm) uniformly covered the surface of NiMoO4 nanorods, acting as an active species and facilitating the surface change transfer to the interior. The internal NiMoO4 cores, on the other hand, provides reliable electron transmission as a highly conductive medium, and can effectively overcome the low conductivity of FeOOH. DFT calculations further manifest the strong electronic interactions between NiMoO4 and FeOOH species. The NiMoO4 core serves as mass transport of active materials is beneficial to tune the adsorption energy of OH− on the surface of electrocatalysts.
Graphene Oxide as a Self‐Carbocatalyst to Facilitate the Ring‐Opening Polymerization of Glycidol for Efficient Polyglycerol Grafting
Authors: Zou Yajuan , Ohkura Kentaro , Ortiz‐Anaya Israel , Kimura Ryota , Bianco Alberto , Nishina Yuta
Published: December 2024

Grafting carbon‐based nanomaterials (CNMs) with polyglycerol (PG) improves their application potentials in biomedicine and electronics. Although “grafting from” method offers advantages over “grafting to” one in terms of operability and versatility, little is known about the reaction process of glycidol with the surface groups onto CNMs. By using graphene oxide (GO) as a multi‐functional model material, we examined the reactivity of the surface groups on GO toward glycidol molecules via a set of model reactions. We reveal that carboxyl groups spontaneously react with the epoxide ring with no need of catalyst, while GO catalyzes the reactions of hydroxyl groups with the epoxide of glycidol. In addition, the hydroxyl group of glycidol can open the epoxide in the basal plane of GO. The subsequent polymerization of PG is supposed to propagate at the primary and/or the secondary hydroxyl groups, generating a ramified PG macromolecule with random branch‐on‐branch topology. In addition, ketones, benzyl esters and aromatic ethers are found not to react with glycidol even in the presence of GO, while the aldehydes are easily oxidized into carboxyl groups under ambient condition, behaving then as the carboxyl groups. Our findings pose the foundation for understanding the polymerization mechanism of PG on CNMs.
The Application of Deuteration Strategy in Drug Design
Authors: Chen Yuzhu , Du Yunfei
Published: December 2024

Deuterated drugs, which are derived from the subtle exchange of a protium atom with a deuterium atom in drug molecules, exhibit significant differences in pharmaceutical characteristics compared to their parent drugs. With the advantages of improving pharmacokinetic properties, reducing toxicity, inhibiting the interconversion between chiral drugs and restricting drug interactions, deuterated drugs have attracted widespread attention from medicinal chemists. This review highlights the application of deuteration strategies in drug design, summarizing the progress of all deuterated drugs available in the market or still under investigation to provide a reference for all researchers engaged deuterated drug development.
Small‐Molecule Fluorescent Probes for Butyrylcholinesterase
Authors: Lin Zibo , Liao Yuanyuan , Tian Donglei , Liao Junyu , Chen Qiong , Yin Jun
Published: December 2024

Butyrylcholinesterase plays an indispensable role in organisms, and its abnormal expression poses a significant threat to human health and safety, covering various aspects including liver‐related diseases, diabetes, obesity, cardiovascular and cerebrovascular diseases, and neurodegenerative diseases. In addition, toxic substances such as organophosphorus and carbamate pesticides markedly inhibit BChE activity. BChE activity serves as a critical parameter for the clinical diagnosis of acute organophosphorus pesticide poisoning and the evaluation of organophosphorus and carbamate pesticide residues. Therefore, the accurate and reliable detection of butyrylcholinesterase activity is particularly urgent and important for in‐depth analysis of its biological function, diagnosis and therapy of related diseases, drug screening and sensitive detection of pesticide residues. Fluorescent probes have become a promising tool for sensing and imaging of butyrylcholinesterase, due to its advantages of high spatio‐temporal resolution, high selectivity, non‐invasive, high sensitivity, and tailored molecule structures. Here, this paper provides a comprehensive overview of the research progress in the sensing, imaging and therapy of butyrylcholinesterase utilizing fluorescent probes. This paper might be a useful guideline for researchers to design new high‐performance fluorescence probes for BChE, and making further contributions to this intriguing field.
Boosting oxygen electrode efficiency using engineered CuO/Cu2O/C nanostructure
Authors: Hazarika Kumar Kashyap , Bhuyan Shaheen Parveez , Chetry Rashmi , Bharali Pankaj
Published: December 2024

The key ongoing challenge is to design and develop effective and inexpensive oxygen reduction reaction (ORR) catalysts to replace Pt‐based ones for commercial use in fuel cells. Owing to its abundance and tunable electronic properties, in the current work, the synthesis of highly dispersed mixed valent copper oxide electrocatalyst is reported. The EC exhibits a high mass activity of 9.8 mA mg−1 and a high current density of 5.3 mA cm−2 in contrast to the benchmark (20 wt%) Pt/C catalyst in a 0.1‐M KOH solution for ORR. The significantly high electrochemical activity at the cathode is believed to be due to the presence of the Cu(II)/Cu(I) redox pair. Furthermore, the catalyst has been shown to be highly stable, maintaining a high current retention of 78% for up to 24 h. Furthermore, the engineered material is also active for the oxygen evolution reaction, making it a viable replacement for conventional Pt/C in alkaline fuel cells.
A Phase 1, Open‐Label, Randomized, Two‐Part Study in Healthy Adult Volunteers to Evaluate the Bioavailability of the Maribavir Powder for Oral Suspension, as Well as Food Effect and Impact of Rabeprazole
Authors: Campagne Olivia , Ilic Katarina , Gabriel Andre , Sueda Katsuhiko , Ye Ran , Zhang Fangqiu , Xu Peixin , Ko Hnin Hnin , Sun Kefeng
Published: December 2024

The relative bioavailability and impact of food and the proton pump inhibitor rabeprazole on the pharmacokinetics of a maribavir powder‐for‐oral‐suspension formulation was investigated in a Phase 1 open‐label study in healthy adult volunteers. A single 200‐mg maribavir dose was administered as the commercial tablet (Treatment A), powder formulation (Treatment B), or powder formulation with a high‐fat/high‐calorie meal (Treatment C) in Part 1, and as the powder formulation alone (Treatment D) or following administration of rabeprazole 20 mg once daily for 5 days (Treatment E) in Part 2. Maribavir maximum plasma concentration following Treatment B was 18% lower versus Treatment A, whereas the area under the concentration‐time curve (AUC) from time 0 to the last quantifiable concentration or infinity were similar. Maribavir maximum plasma concentration, AUC from time 0 to the last quantifiable concentration, and AUC from time 0 to infinity were reduced by 42%, 18%, and 18% (Treatment C vs Treatment B), and by 51%, 30%, and 11% (Treatment E vs Treatment D), respectively. A clinically significant reduction in maribavir exposure is not expected when maribavir powder formulation is taken with food or proton pump inhibitors. Participants assessed the powder for oral suspension as easy to swallow and having an acceptable taste/texture. Safety profiles for maribavir formulations in this study were consistent with those previously published.
Leptin and Associated Neural Pathways Underlying Obesity‐Induced Hypertension
Authors: Laule Connor , Rahmouni Kamal
Published: December 2024

Obesity rates have surged to pandemic levels, placing tremendous burden on our society. This chronic and complex disease is related to the development of many life‐threatening illnesses including cardiovascular diseases. Hypertension caused by obesity increases the risk for cardiovascular mortality and morbidity by promoting stroke, myocardial infarction, congestive heart failure, and end‐stage renal disease. Overwhelming evidence supports neural origins for obesity‐induced hypertension and pinpoints the adipose‐derived hormone, leptin, and the sympathetic nervous system as major causal factors. Hyperleptinemia in obesity is associated with selective leptin resistance where leptin's renal sympathoexcitatory and pressor effects are preserved while the metabolic actions are impaired. Understanding the mechanisms driving this phenomenon is critical for developing effective therapeutics. This review describes the neural mechanisms of obesity‐induced hypertension with a focus on the molecular and neuronal substrates of leptin action.
Enhanced Simulation of Complicated MXene Materials with Graph Convolutional Neural Networks
Authors: Chen Xin , Wan Zicheng , Lao Sisi , Tian Ziqi
Published: December 2024

MXene, a notable two‐dimensional transition metal carbide, has attracted increasing attention in materials science due to its unique attributes, driving innovations in energy storage, sensors, catalysts, and electromagnetic shielding. The property and application performance are determined by the electronic structure, which can be described based on the density of states (DOS). The conventional density functional theory (DFT) calculation is able to provide the DOS spectrum of a specific atomic structure. However, for complicated composition, such as the recently reported high entropy MXene, the DFT calculations in exhaustive structure space are resource‐intensive. In this study, machine learning (ML) technique, specifically the crystal graph convolutional neural networks (CGCNN) model, is applied to generate DOS of these MXene models with complex compositions. By using calculations on M3C2 and M4C3 structures as training sets, the DOS of the complex high entropy MXene is well reproduced according to the atomic structure. Moreover, the adsorption energy of lithium is precisely predicted based on the DOS, which can be further employed to screen the potential electrode materials for lithium batteries. Herein, ML method not only streamlines predictions but also enhances the understanding of MXene's intrinsic properties.
Foxing of Watercolor Paper and Environmental Control as Preventive Actions
Authors: Ng Woon Lam , Hu Huanlong , Zhuang Zeyan
Published: December 2024

In Singapore's hot and humid climate, watercolor papers are particularly prone to a paper oxidation issue known as foxing, which refers to the discoloration forming yellowish‐brown stains on paper, changing the visual outcome of the watercolor artworks. This research investigates two most popular types of watercolor paper, made from 100 % cotton and cotton‐wood‐pulp mixture. Foxing was generally categorized into two types: biotic and abiotic foxing caused by fungi activities and the presence of metallic contaminants catalytic fungi growth. However, recent hypotheses further relate it to heterogeneous cellulose structures. Watercolor paper is typically produced in a well‐controlled environment, which should theoretically reduce the occurrence of foxing, catalyzed by metallic contaminants. The research involved a comprehensive analysis of aged samples, from old watercolors, dating back to the 1990s and fresh watercolor paper samples. focusing on understanding the origin and causes of watercolor paper foxing based on cellulose content & structures. By comparing 100 % cotton and cotton wood‐pulp blended watercolor paper, the susceptivity of foxing was hinted to be related to cellulose packing density. These findings will support further research in developing strategies for the conservation and storage of watercolor artworks.
Purple Bacteria Reaction Center Based Solid State Bio‐Solar Cell With a Large Open Circuit Voltage
Authors: Tulus Tulus , Friebe Vincent Morris , Peukert Andreas , Muscarella Loreta A. , Jones Michael R. , Frese Raoul N. , von Hauff Elizabeth
Published: December 2024

A novel solid state bio‐solar cell is demonstrated based on a purple bacterial reaction center‐light harvesting 1 complex (RC‐LH1) that exhibits high quantum efficiency and long carrier lifetimes. We demonstrate that careful choice of transport layers enables a high open circuit voltage of up to 0.3 V in these solid state biophotovoltaic devices. Electronic processes were investigated with impedance spectroscopy. Equivalent circuit modelling of impedance spectra obtained under illumination at DC offset voltages between open circuit and short circuit conditions revealed two relaxations on microsecond and millisecond time scales that are attributed to the charge transit time and carrier recombination processes, respectively. The operational stability of the solar cells was examined under constant illumination for over 3 hours and a burn‐in time of several minutes was observed, after which operational parameters stabilized. This work is the largest voltage reported for RC‐LH1 based solid state biophotovoltaic devices to date.
Aprotic Electrolytes Beyond Organic Carbonates: Transport Properties of LiTFSI Solutions in S‐Based Solvents
Authors: Piacentini Vanessa , Simari Cataldo , Mangiacapre Emanuela , Pierini Adriano , Gentile Antonio , Marchionna Stefano , Nicotera Isabella , Brutti Sergio , Bodo Enrico
Published: December 2024

This work illustrates a physico‐chemical study of the structural, dynamic, and transport properties of electrolytes made of LiTFSI solutions in sulphoxide and sulphone solvent mixtures. Experimental measurements, by Raman and NMR spectroscopies, as well as electrochemical impedance spectroscopy, reveal the formation of a variety of ionic aggregates depending on the solvent composition that significantly affect the ion mobility and conductivity of the electrolyte. Mixtures containing tetrahydrothiophene‐1‐oxide exhibit a larger ion mobility due to a rapid exchange mechanism between solvent molecules, whereas the use of tetramethylene sulphone favors the formation of ionic aggregates due to the strong dipolar interactions between solvent molecules.