bluuebunny/crossref_metadata_2025 huggingface dataset:
Copper‐Catalyzed Aerobic Cross‐Dehydrogenation Coupling of Indoles for Synthesis of 2,3′‐Bisindoles
Authors: Huang Xinxiang , Yang Yingying , He Qiping , Liu Chang , Yuan Mingquan , Jin Yi
Published: September 2024

2,3’‐Bisindoles with C−C linkages have attracted interest in medicinal chemistry, yet their synthesis is intricate with many steps. Notably, direct C−H/C−H cross‐coupling of non‐directed heteroaromatics remains challenging, often requiring precious metals and oxidants to enhance coupling efficiency. Herein, we present a copper‐catalyzed C−H/C−H cross‐coupling method for N‐substituted indoles without directing groups, facilitated by molecular oxygen under gentle conditions. It showed reasonable functional group compatibility and provided one‐pot access to a variety of 2,3′‐bisindoles derivatives in moderate to good yields.
Mechanistic Perspectives: Integration and Repairing Adaptation of Self‐Healing Electrolytes for Zinc Ion Batteries
Authors: Arif Muhammad , Yang Liujuan , Zhang Qi , Wang Haiyan
Published: September 2024

Self‐healing is a magical function that endows energy storage devices with extraordinary resilience and has become a promising strategy for advancing battery technology. This short review focus on the recent developments made in self‐healing chemistry for electrolytes in term of extrinsic and intrinsic dynamical concepts. Firstly, the fundamental mechanism of electrolyte self‐healing and repairing adaptation is introduced. The extrinsic self‐healing mechanism adopts capsule‐vascular networking while intrinsic self‐healing lean physical and chemical routes. The Former healing adaptation, generally follows strong physical networking and covalent linkages, which are more prevalent and practical, compared to the latter case of self‐healing. In addition to that, this review also evaluates the estimated healing capabilities and statistics using thermodynamic protocols. Finally, we propose some possible future research directions and development strategies to further apply the self‐healing phenomenon for zinc ion batteries.
Altered glycosylation in cancer: molecular functions and therapeutic potential
Authors: Xu Xuemeng , Peng Qiu , Jiang Xianjie , Tan Shiming , Yang Wenjuan , Han Yaqian , Oyang Linda , Lin Jinguan , Shen Mengzhou , Wang Jiewen , Li Haofan , Xia Longzheng , Peng Mingjing , Wu Nayiyuan , Tang Yanyan , Wang Hui , Liao Qianjin , Zhou Yujuan
Published: September 2024

Glycosylation, a key mode of protein modification in living organisms, is critical in regulating various biological functions by influencing protein folding, transportation, and localization. Changes in glycosylation patterns are a significant feature of cancer, are associated with a range of pathological activities in cancer‐related processes, and serve as critical biomarkers providing new targets for cancer diagnosis and treatment. Glycoproteins like human epidermal growth factor receptor 2 (HER2) for breast cancer, alpha‐fetoprotein (AFP) for liver cancer, carcinoembryonic antigen (CEA) for colon cancer, and prostate‐specific antigen (PSA) for prostate cancer are all tumor biomarkers approved for clinical use. Here, we introduce the diversity of glycosylation structures and newly discovered glycosylation substrate—glycosylated RNA (glycoRNA). This article focuses primarily on tumor metastasis, immune evasion, metabolic reprogramming, aberrant ferroptosis responses, and cellular senescence to illustrate the role of glycosylation in cancer. Additionally, we summarize the clinical applications of protein glycosylation in cancer diagnostics, treatment, and multidrug resistance. We envision a promising future for the clinical applications of protein glycosylation.
The Catalytic Mechanism of Decarboxylation of L‐DOPA to Dopamine by Papaver somniferum Aromatic Amino Acid Decarboxylase – A Computational Study
Authors: Sousa João P. M. , Ramos Maria J. , Fernandes Pedro A.
Published: September 2024

Morphine and codeine are essential medicines isolated from the opium poppy, whose biosynthesis is limited by the plant's L‐DOPA decarboxylase activity. In the present study, we use molecular dynamics and hybrid quantum mechanics/ molecular mechanics calculations to clarify the L‐DOPA decarboxylase chemical mechanism of decarboxylation and quinonoid intermediate protonation. In addition, the contribution of residues in the periphery of the active site to the rate‐limiting decarboxylation barrier was determined to guide future experimental mutagenesis aimed at increasing the catalytic activity of the aromatic amino acid decarboxylase enzyme, a fundamental step for the opiumpoppy‐free production of BIAs. Our calculations indicate that the decarboxylation barrier is higher in conformations in which the interaction between Tyr350B and the carboxylate leaving group is formed. Furthermore, the barrier for the protonation of the quinonoid intermediate by Tyr350B is predicted to be lower than the decarboxylation and dependent on His205A protonation by the bulk solvent. Residues Glu171, Asp270, Asp313 and Arg482 were identified as possible candidates for rate‐enhancing mutations of P. somniferum aromatic amino acid decarboxylase.
Exploring Dry Reforming of CH4 to Syngas Using High‐Entropy Materials: A Novel Emerging Approach
Authors: Bhaskaran Aathira , Roy Sounak
Published: September 2024

The high global warming potential of natural gas methane necessitates its conversion into valuable products, typically through syngas production. Among various technologies for methane valorization, dry reforming of methane (DRM), particularly when integrated with carbon capture, stands out as a prominent method. However, persistent challenges such as the reverse water‐gas shift reaction, coke formation, and sintering associated with methane dry reforming have redirected scientific focus toward multimetallic catalysts with supports or promoters. High‐entropy materials have gained attention as promising catalysts because their flexible composition allows fine‐tuning of lattice oxygen reactivity and catalytic activity. Entropy plays a key role in catalysis, and recent research focuses on the enthalpy–entropy relationship that influences reaction pathways. Alongside entropy, core effects like lattice distortion, sluggish diffusion, and cocktail effects improve catalytic performance by synergistic effects, prevent carbon buildup, and maintain stability at high temperatures, enabling efficient methane conversion. These advancements in high‐entropy materials drive interest in using entropy‐stabilized systems to address the challenges of methane dry reforming. This review summarizes recent advancements in the dry reforming of methane, particularly the integration of carbon capture techniques with dry reforming processes using high‐entropy materials.
Two‐Dimensional (2D) Conductive Metal‐Organic Framework Thin Films: The Preparation and Applications in Electrochemistry.
Authors: Liu Wentao , Yuan Guoqiang , Jiang Shu , Shi Yuxin , Pang Huan
Published: September 2024

Two‐dimensional conductive MOF thin films have attracted attention due to their rich pore structure and unique electrical properties, and their applications in many fields, including batteries, sensing, supercapacitors, electrocatalysis, etc. This paper discusses several preparation methods for 2D conductive MOF thin films. And the applications of 2D conductive MOF thin films are summarized. In addition, the current challenges in the preparation of 2D conductive MOF thin films and the great potential in practical applications are discussed.
50 Years of Organoselenium Chemistry, Biochemistry and Reactivity: Mechanistic Understanding, Successful and Controversial Stories
Authors: Madabeni Andrea , Bortoli Marco , Nogara Pablo A. , Ribaudo Giovanni , Dalla Tiezza Marco , Flohé Leopold , Rocha João B. T. , Orian Laura
Published: September 2024

In 1973, two major discoveries changed the face of selenium chemistry: the identification of the first mammal selenoenzyme, glutathione peroxidase 1, and the discovery of the synthetic utility of the so‐called selenoxide elimination. While the chemical mechanism behind the catalytic activity of glutathione peroxidases appears to be mostly unveiled, little is known about the mechanisms of other selenoproteins and, for some of them, even the function lies in the dark. In chemistry, the capacity of organoselenides of catalyzing hydrogen peroxide activation for the practical manipulation of organic functional groups has been largely explored, and some mechanistic details have been clearly elucidated. As a paradox, despite the long‐standing experience in the field, the nature of the active oxidant in various reactions still remains matter of debate. While many successes characterize these fields, the pharmacological use of organoselenides still lacks any true application, and while some organoselenides were found to be non‐toxic and safe to use, to date no therapeutically approved use was granted. In this review, some fundamental and chronologically aligned topics spanning organoselenium biochemistry, chemistry and pharmacology are discussed, focusing on the current mechanistic picture describing their activity as either bioactive compounds or catalysts.
The erosion of rationality in high vulnerability conditions: A cognitive‐disruption perspective
Authors: Freling Traci , Saini Ritesh , Yang Zhiyong
Published: September 2024

This research examines how a decision‐maker's perceived vulnerability influences their susceptibility to the “anecdotal bias,” a phenomenon where statistical evidence is disregarded in favor of anecdotal information. Across six studies, our research shows that high vulnerability aggravates the anecdotal bias instead of reducing it. Study 1 provides preliminary evidence that high vulnerability exacerbates the anecdotal bias among individuals seeking decision‐relevant information in the context of the COVID‐19 pandemic. Studies 2A and 2B demonstrate that high vulnerability intensifies the anecdotal bias in different decision contexts. Study 3 replicates these findings and identifies negative emotional arousal as a key mechanism underlying this effect. Study 4 examines the moderating role of personal relevance, showing that when individuals make decisions for others (vs. themselves), high vulnerability does not lead to the anecdotal bias. Moreover, it is cognitive disruption and intuitive thinking caused by negative emotional arousal that increases reliance on anecdotal (vs. statistical) information. Finally, Study 5 demonstrates the moderating effect of mindfulness meditation, highlighting its role as a preemptive safeguard against this biased behavior. Theoretical contributions and practical implications of these findings are discussed.
F‐actin in the cuticular plate and junctions of auditory hair cells is regulated by ADF and cofilin to allow for normal stereocilia bundle patterning and maintenance
Authors: McGrath Jamis , Hawbaker Katelin , Perrin Benjamin J.
Published: September 2024

Auditory hair cells, which convert sound‐induced vibrations in the inner ear into neural signals, depend on multiple actin populations for normal function. Stereocilia are mechanosensory protrusions formed around a core of linear, crosslinked F‐actin. They are anchored in the cuticular plate, which predominantly consists of randomly oriented actin filaments. A third actin population is found near hair cell junctions, consisting of both parallel and branched filaments. Actin depolymerizing factor (ADF) and cofilin‐1 (CFL1) proteins disassemble actin filaments and are required to regulate F‐actin in stereocilia, but their effect on cuticular plate and junctional actin populations is unclear. Here, we show that loss of ADF and CFL1 disrupts the patterning of stereocilia into orderly bundles and that this phenotype correlates with defective development of the cuticular plate and junctional actin populations. ADF/CFL1 continue to regulate these actin populations in mature cells, which is necessary for long‐term maintenance of hair cell morphology.
Nonsentinel lymph node metastases in cases of micrometastasis detected by sentinel lymph node biopsy after neoadjuvant chemotherapy
Authors: Shin Dong Seung , Ryu Jai Min , Lee Se Kyung , Yu Jonghan , Lee Jeong Eon , Kim Seok Won , Nam Seok Jin , Chae Byung Joo
Published: September 2024

Background

There is a clinical need to omit axillary lymph node dissection (ALND) when residual disease in sentinel lymph nodes (SLNs) is low after neoadjuvant chemotherapy (NAC). This study aimed to clarify the relationship between micrometastasis in SLNs after NAC and additional non‐SLN metastases by analyzing SLN biopsy results followed by ALND.

Methods

This retrospective study reviewed clinical records of patients who underwent breast cancer surgery between January 2010 and June 2022 after NAC at Samsung Medical Center. Of 3944 patients, 806 underwent SLN biopsy followed by ALND. Intraoperative frozen SLN biopsy results were examined, including the number and size of metastases in SLNs, and further investigated the number of additional non‐SLN metastases.

Results

Among the 806 patients, 95 (11.8%) had micrometastasis on SLNs in frozen sections, of which 89 (93.7%) had clinically node‐positive (cN1‐3) breast cancer before NAC. Twenty‐three patients (24.2%) exhibited positive additional non‐SLNs after ALND. The presence of lymphovascular invasion (vs. absence; odds ratio [OR] = 4.02, p = .0151) and having two or more SLNs with micrometastasis (vs. a positive SLN; OR = 3.65, p = .0301) were significantly associated with additional non‐SLN metastases. Tumor subtypes and breast pathological complete response after NAC showed no correlation with the additional non‐SLN metastases.

Conclusion

The study identified a 24.2% possibility of additional non‐SLN metastasis if micrometastases was detected in the SLN after NAC. This rate is significant, indicating that ALND cannot be omitted if low volume residual disease, such as micrometastasis, is identified in the SLN after NAC.
Aromaticity and Antiaromaticity Reversals between the Electronic Ground State and the Two Lowest Triplet States of Thiophene
Authors: Cummings Edward , Karadakov Peter B.
Published: September 2024

It is shown, by examining the variations in off‐nucleus isotropic magnetic shielding around a molecule, that thiophene which is aromatic in its electronic ground state (S0) becomes antiaromatic in its lowest triplet state (T1) and then reverts to being aromatic in T2. Geometry relaxation has an opposite effect on the aromaticities of the ππ* vertical T1 and T2: The antiaromaticity of T1 is reduced whereas the aromaticity of T2 is enhanced. The shielding picture around T2 is found to closely resemble those around certain second singlet ππ* excited states (S2), for example, those of benzene and cyclooctatetraene, thought to be “strongly aromatic” because of their very negative nucleus‐independent chemical shift (NICS) values. It is argued that while NICS values correctly follow the changes in aromaticity along the potential energy surface of a single electronic state, the use of NICS values for the purpose of quantitative comparisons between the aromaticities of different electronic states cannot be justified theoretically and should be avoided. “Strongly aromatic” S2 and T2 states should be referred to simply as “aromatic” because detailed comparisons between the properties of these states and those of the corresponding S0 states do not suggest higher levels of aromaticity.
4,4′‐Sulfonyldianiline Derived Aggregation‐Induced Emission Luminogen for the Detection of Ofloxacin
Authors: Patel Dhvani A. , Anand Thangaraj , Jali Bigyan R. , Sahoo Suban K.
Published: September 2024

The excessive use of antibiotic ofloxacin (Oflx) can cause serious detrimental effects to human health. Therefore, the utmost research priority is required to develop facile methods to detect Oflx. Herein, a V‐shaped aggregation‐induced emission (AIE) active Schiff base SDANA was introduced for the fluorescent turn‐on detection of Oflx. The Schiff base SDANA was synthesized by condensing 4,4′‐sulfonyldianiline with two equivalents of 2‐hydroxy‐1‐naphthaldehyde. The nearly non‐fluorescent SDANA in DMSO showed strong orange emission with the increase in HEPES buffer (H2O, 10 mM, pH 7.4) fractions in DMSO from 70 %–95 % due to the combined effects of AIE and ESIPT. The DLS and SEM analyses were performed to complement the formation of self‐aggregates of SDANA. With the addition of Oflx, the fluorescence emission of AIE luminogen (AIEgen) SDANA (λem=575 nm, λex=400 nm) was blue‐shifted and enhanced at 530 nm. The interactions of Oflx over the surface of SDANA aggregates disrupted the intramolecular charge transfer and aggregation morphology of SDANA, which gave a distinct fluorescence response to detect Oflx. The detection limit for Oflx was estimated as 0.81 μM, and the developed probe AIEgen SDANA was applied for the quantification of Oflx in human blood serum.
Room‐Temperature Columnar Tetragonal Self‐Assemblies based on Benzenetricarboxamide and Di‐ortho Substituted Azobenzene
Authors: Krishna KM Abhinand , Gupta Monika
Published: September 2024

Here we report the design, synthesis, and photoresponsive behavior of supramolecular liquid crystalline (LC) materials based on benzenetricarboxamide and di‐ortho substituted azobenzene. Differential scanning calorimetry, polarized optical microscopy, and wide‐angle X‐ray scattering studies confirm the formation of columnar tetragonal mesophase at room‐temperature. Photoisomerization studies reveal the visible light responsiveness of compounds in solution. Furthermore, we demonstrate supramolecular gel formation, which undergoes irreversible gel‐sol transformation upon blue light irradiation, highlighting its potential for light‐triggered applications in the field of drug delivery, energy storage etc.
Visible‐Light Induced Selective C−H Arylation of 2‐Imino‐2H‐Chromene‐3‐Carbonitriles and Decarboxylative Ipso‐Arylation of 2‐Oxo‐2H‐Chromene‐3‐Carboxylic Acids
Authors: Sahoo Tanmoy , Banik Swarnayu , Vijaya Prasanna Dasari , Sridhar B. , Subba Reddy B. V.
Published: September 2024

Visible‐light induced selective arylation of 2‐imino‐2H‐chromene‐3‐carbonitriles and decarboxylative ipso‐arylation of coumarin‐3‐carboxylic acids have been accomplished under mild conditions in the absence of either base or acid and oxidant. By employing blue LEDs as an excitation source, the aryl radicals are generated by Ru(II) complex through a single‐electron transfer process, which subsequently react with 2‐imino‐2H‐chromene‐3‐carbonitriles and 2‐oxo‐2H‐chromene‐3‐carboxylic acids to produce the desired products. This is the first report on selective arylation of conjugated systems without using either an acid or a base.
Lignin Nanofiber Flexible Carbon Aerogels for Self‐Standing Supercapacitors
Authors: Cho MiJung , Yiu Justine , Lin Li‐Ting , Hua Qi , Karaaslan Muzaffer A. , Renneckar Scott
Published: September 2024

Renewable feedstocks are sought for clean technology applications, including energy storage applications. In this study, LignoForce™ lignin, a biobased aromatic polymer commercially isolated from wood, was fractioned into two parts using acetone, and the resulting lignin fractions had distinct thermo‐rheological behavior. These two fractionated lignins were combined in various ratios and transformed into nanofibers by electrospinning. Subsequently, electrospun fiber materials were disrupted by agitating the mats in water, and the materials were transformed into ultralight 3D aerogels through lyophilization and post‐process controlled heating. Using only this combination of two fractions, the morphology of lignin nanofibers was tailored by heat treatment, resulting in lignin aerogels with high flexibility and significant shape recovery properties. Various microscale structures of lignin fibers impacted the resulting physical properties of the elastic aerogel materials, such as resilience, compressive strength, and electrical conductivity for the corresponding carbonized samples. By exploiting lignin's sensitivity to heat and tailoring the thermal properties of the lignin through fractionation, the work provided an interesting path to form robust lignin‐derived functional materials without any toxic chemical additives and significant ability to serve as free‐standing electrodes with specific capacitance values better than some graphene‐based supercapacitors.
Activated Carbon Fiber Felt Composites for the Direct Air Capture of Carbon Dioxide
Authors: Korah Mani Modayil , Culp Kyle , Lackner Klaus S. , Green Matthew D.
Published: September 2024

Negative emissions technologies to mitigate climate change require innovative solutions for the direct air capture (DAC) of CO2 from the atmosphere. K2CO3 readily reacts with CO2 to form KHCO3; however, bulk K2CO3 suffers from very slow sorption kinetics. By incorporating K2CO3 into activated carbon (AC) fiber felts, the sorption kinetics were significantly improved by increasing the surface area of K2CO3 in contact with air. The AC‐K2CO3 fiber composite felts are flexible, cheap, easy to manufacture, chemically stable, and show excellent DAC capacity and (de)sorption rates, with stable performance up to ten cycles. Cyclic testing was demonstrated with 4 h sorption and 0.5 h desorption intervals. The best composite felts collected an average of 478 μmol of CO2 per gram of composite during 4 h of exposure to ambient air (19 % relative humidity) that had a CO2 concentration of 400–450 ppm after regeneration at 125 °C in an air furnace. An increase in the dew point temperature from 0 to 12 °C decreased sorption performance of the composite felts by 40 %.
Understanding the Roles and Regulation Methods of Key Adsorption Species on Ni‐Based Catalysts for Efficient Hydrogen Oxidation Reactions in Alkaline Media
Authors: Li Jinchi , Yu Shuqi , Qing Chen , Wang Yao , Chen Yungui
Published: September 2024

This review focuses on recent advancements in the development and understanding of nickel‐based catalysts for the hydrogen oxidation reaction in alkaline media. Given the economic and environmental limitations associated with platinum group metals, nickel‐based catalysts have emerged as promising alternatives due to their abundance, lower cost, and comparable catalytic properties. The review begins with an exploration of the fundamental HOR mechanisms, emphasizing the key roles of the reactive species in optimizing the catalytic activity of Ni‐based catalysts. Thermodynamic and stability optimizations of nickel‐based catalysts are thoroughly examined, focusing on alloying strategies, heteroatom incorporation, and the use of various support materials to enhance their catalytic performance and durability. The review also addresses the challenge of catalyst poisoning, particularly by carbon monoxide, and evaluates the effectiveness of different approaches to improve poison resistance. Finally, the review concludes by summarizing the key findings and proposing future research directions to further enhance the efficiency and stability of nickel‐based catalysts for practical applications in anion exchange membrane fuel cells. The insights gained from this comprehensive analysis aim to contribute to the development of cost‐effective and sustainable catalysts and facilitate the broader adoption of AEMFCs in the quest for clean energy solutions.
Review of Ni‐Based Materials for Industrial Alkaline Hydrogen Production
Authors: Chen Cong , Olu Pierre‐Yves , Fan Ronglei , Shen Mingrong
Published: September 2024

Hydrogen has been recognized as a green energy carrier, which can relieve energy shortage and environmental pollution. Currently, alkaline water electrolysis (AWE) driven by renewable energy to produce large‐scale green hydrogen is a mainstream technology. However, tardy cathodic hydrogen evolution reaction (HER) and stability issue of catalysts make it challenging to meet the industrial requirements. Ni‐based materials have attracted wide attention, thanks to their low cost and rich tuning possibilities, and many efforts have focused on their activity and stability. However, due to the significant discrepancy between laboratory and industrial conditions, these catalysts have not been widely deployed in industrial AWE. In this review, we first introduce the differences between laboratory and industrial stage, especially concerning equipment, protocols and evaluation metrics. To shorten these gaps, some strategies are proposed to improve the activity and stability of the Ni‐based catalysts. Besides, some key issues related to the catalysts in industrial AWE device are also emphasized, including reverse‐current and foreign ions in the electrolyte. Finally, the challenges and outlooks on the industrial alkaline AWE are discussed.
Co@NC Chainmail Nanowires for Thermo‐ and Electrocatalytic Oxidation of 2,5‐Bis(hydroxymethyl)furan to 2,5‐Furandicarboxylic Acid
Authors: Zhu Bin , Wang Qiuge , Wang Jinggang , Yu Xiao , Zhang Jian , Chen Chunlin
Published: September 2024

2,5‐Furandicarboxylic acid (FDCA) has emerged as an important bio‐based furanic compound, which has broad application prospects in renewable energy and materials, especially in the preparation of polyethylene 2,5‐furandicarboxylate (PEF). While the conventional synthesis of FDCA involves oxidation of 5‐hydroxymethylfurfural (HMF) as a substitute, the thermal and chemical instability of HMF due to its aldehyde group poses challenges. A more favorable alternative is the utilization of 2,5‐bis(hydroxymethyl)furan (BHMF), a non‐aldehyde and more stable precursor. This study pioneeringly reports nitrogen‐doped‐carbon encapsulated cobalt (Co@NC) chainmail nanowires for the thermal and electrocatalytic oxidation of BHMF to FDCA. The Co@NC/NF achieved a 97.9 % conversion of BHMF with a 93.3 % yield of FDCA at 1.475 V vs. RHE, whereas thermal catalysis only obtained 14.9 % FDCA yield after 10 hours. Kinetic studies indicated that the large electrochemically active surface area and excellent kinetic parameters contribute its superior electrochemical performance. Mechanistic analysis revealed that the migration of inner electrons to the exterior modified the electronic properties of the carbon layer, thereby facilitating the oxidation of BHMF. Furthermore, the in‐situ generation of high‐valent cobalt species markedly accelerated the BHMF oxidation. This research underscores the potential of carbon‐encapsulated metal chainmail catalysts in thermal and electrochemical biomass conversion.
Chemoselective Intramolecular Rauhut‐Currier Reaction on a Labile Framework of Enone and Acrylamide: Tricyclohexylphosphine as a Stable and Economical Catalyst
Authors: Verma Rakesh Kumar , Bairwa Mansingh , Bharadwaj Kishor Chandra
Published: September 2024

Intramolecular Rauhut‐Currier (IRC) reaction is an atom‐economical way of making carbocyclic and heterocyclic rings. However, its sensitivity towards electronic and steric parameters limits the reaction and stems the need for further development. Acrylamides have been one such left out of their sensitivity. Herein we report an IRC reaction, using acrylamide as a source of initial enolate. The cyclization has been achieved on a labile and challenging framework, prone to decomposition. Different control experiments have addressed the instability of the precursor. Protocol was further extendable to annulation for benzo analogs. We also report tricyclohexylphosphine (PCy3) as a stable, commercial, and easy‐to‐use nucleophilic catalyst in the field of IRC reactions as compared to earlier well‐established trimethyl and tributyl phosphines. Me3P and Bu3P although useful, are sensitive, prone to oxidation, and need careful handling. The protocol leads to the synthesis of piperidone and dihydroquinolone frameworks. A quick study to test the feasibility of catalyzing the Morita‐Baylis‐Hillman (MBH) reaction by PCy3 was also done successfully, although in moderate yields.
The application of match‐event and instrumented mouthguard data to inform match limits: An example using rugby union Premiership and rugby league Super League data from England
Authors: Sawczuk Thomas , Cross Matt , Owen Cameron , Roe Gregory , Stokes Keith , Kemp Simon , Tooby James , Allan David , Falvey Éanna , Starling Lindsay , Tierney Gregory , Tucker Ross , Jones Ben
Published: September 2024

The study aimed to illustrate how contact (from match‐event data) and head acceleration event (HAE) (from instrumented mouthguard [iMG]) data can be combined to inform match limits within rugby. Match‐event data from one rugby union and rugby league season, including all competitive matches involving players from the English Premiership and Super League, were used. Playing exposure was summarised as full game equivalents (FGE; total minutes played/80). Expected contact and HAE exposures at arbitrary thresholds were estimated using match‐event and iMG data. Generalised linear models were used to identify differences in contact and HAE exposure per FGE. For 30 FGEs, forwards had greater contact than backs in rugby union (n = 1272 vs. 618) and league (n = 1569 vs. 706). As HAE magnitude increased, the differences between positional groups decreased (e.g., rugby union; n = 34 and 22 HAE >40 g for forwards and backs playing 30 FGEs). Currently, only a relatively small proportion of rugby union (2.5%) and league (7.3%) players exceeded 25 FGEs. Estimating contact and HAEs per FGE allows policymakers to prospectively plan and model estimated overall and position‐specific loads over a season and longer term. Reducing FGE limits by a small amount would currently only affect contact and HAE exposure for a small proportion of players who complete the most minutes. This may be beneficial for this cohort but is not an effective HAE and contact exposure reduction strategy at a population level, which requires individual player management. Given the positional differences, FGE limits should exist to manage appropriate HAE and contact exposure.
Sleep‐related hypermotor seizures originating from the occipital lobe
Authors: Wadi Lara , Khweileh Mays , Agashe Shruti , Southwell Derek , Parikh Prachi , Frauscher Birgit
Published: September 2024

We present two unique cases of sleep‐related hypermotor epilepsy (SHE) originating from the occipital lobe. Patients with sleep‐related seizures and drug‐resistant occipital lobe epilepsy were identified from the ANPHY lab stereo‐electroencephalography (SEEG) research database at the Duke Comprehensive Epilepsy Center. We identified two young females with frequent sleep‐related focal seizures and occasional focal to bilateral tonic clonic seizures characterized by hypermotor movements. During wakefulness, the semiology also involved an elementary visual aura. They meet the 2016 diagnostic criteria for SHE, and SEEG monitoring with cortical stimulation mapping identified an epileptogenic zone (EZ) within the occipital lobe, with most seizures occurring out of NREM 2 sleep. Responsive neurostimulation devices were implanted, which indicated a trend for event detections in nocturnal periods. Extrafrontal SHE has characteristically been described in the temporal, insular‐opercular, and parietal lobes. Here, we demonstrate using SEEG‐confirmed EZ identification, that SHE can also originate in the occipital lobe. In patients with sleep‐related seizures and hypermotor behavior, occipital lobe seizures thus should not be excluded from the differential diagnosis. Key in identifying this rare localization is non‐frontal aura semiology and delay to motor symptoms, which may be supported by a visual field deficit and structural MRI abnormality.
Holocene hillslope evolution through extreme rainfall induced landslides in the mountainous region of Rio de Janeiro, Brazil: Geochronology and paleoenvironmental evidence
Authors: Facadio Ana Carolina , Coelho Netto Ana Luiza , Macario Kita Damasio , Ishimine Karoline Mayume , Barth Ortrud Monika , Jou Renata
Published: September 2024

Geomorphological, geochronological and paleoenvironmental data were integrated to examine how Holocene environmental changes have influenced geomorphic responses, particularly recurrent landslides and colluvial deposition on the steep slopes of the Rio de Janeiro mountains. This study focuses on a pilot hillslope (32°) with a concave‐up topographic hollow and associated shallow translational landslides, enhancing our understanding of how extreme climatic events shaped landscape evolution in the region prior to significant human impact. Recently, the hillslope was reactivated by a shallow landslide triggered by the extreme rainfall event of January 2011, which resulted in over 3600 landslides in the region. Subsequent deep gullying exposed a deposit (>3 m) containing buried, organic‐rich colluvial layers. Comprehensive analysis was conducted on sedimentological, geochronological (AMS 14C), palynological, taphonomic and carbon isotope (δ13C) data from this deposit. The geochronological results indicate that the hillslope's evolution involves recurrent shallow translational landslides throughout the Holocene, with organic colluvial layers dating from 10 148 cal years BP at the base to 663 cal years BP at the top. Charcoal fragments of various sizes suggest frequent paleofires during the Holocene. Palynological and taphonomic analyses reveal post‐fire herbaceous‐shrubby vegetation and ferns (Asteraceae, Poaceae, Alchornea, Baccharis, Celtis and Polypodium), with predominant pollen grains and spores showing mechanical damage indicative of high transport energy and physical stress conditions. The rarefied post‐fire vegetation and pioneer forest genera identified in the deposit are associated with a hydrological and mechanical dynamics that likely created less stable conditions on the slope system, promoting the occurrence of shallow landslides throughout the Holocene.
A combined DTI‐fMRI approach for optimizing the delineation of posteromedial versus anterolateral entorhinal cortex
Authors: Syversen Ingrid Framås , Reznik Daniel , Witter Menno P. , Kobro‐Flatmoen Asgeir , Navarro Schröder Tobias , Doeller Christian F.
Published: September 2024

In the entorhinal cortex (EC), attempts have been made to identify the human homologue regions of the medial (MEC) and lateral (LEC) subregions using either functional magnetic resonance imaging (fMRI) or diffusion tensor imaging (DTI). However, there are still discrepancies between entorhinal subdivisions depending on the choice of connectivity seed regions and the imaging modality used. While DTI can be used to follow the white matter tracts of the brain, fMRI can identify functionally connected brain regions. In this study, we used both DTI and resting‐state fMRI in 103 healthy adults to investigate both structural and functional connectivity between the EC and associated cortical brain regions. Differential connectivity with these regions was then used to predict the locations of the human homologues of MEC and LEC. Our results from combining DTI and fMRI support a subdivision into posteromedial (pmEC) and anterolateral (alEC) EC and reveal a confined border between the pmEC and alEC. Furthermore, the EC subregions obtained by either imaging modality showed similar distinct whole‐brain connectivity profiles. Optimizing the delineation of the human homologues of MEC and LEC with a combined, cross‐validated DTI‐fMRI approach allows to define a likely border between the two subdivisions and has implications for both cognitive and translational neuroscience research.
Postmarketing adverse events of tamoxifen in male and female patients with breast cancer
Authors: Ke Chengjie , Chen Maohua , Lin Li , Huang Yaping
Published: September 2024

Tamoxifen (TAM), a selective estrogen receptor (ER) modulator, has received approval for use in patients with breast cancer (BC) exhibiting positive ER expression. Given the widespread clinical use of TAM, a comprehensive real‐world study of its adverse events (AEs) is warranted. The database for analysis, sourced from the Food and Drug Administration Adverse Event Reporting System (FAERS), covers the period from the first quarter of 2014 to the third quarter of 2023. A disproportionality analysis was conducted to quantify the correlation between TAM and AEs. Subgroup analyses were performed to identify differences between BC AEs in males and females receiving TAM, aiming to assess the risk factors of male BC AEs. Total 4890 reports indicated BC, with 91 and 4190 specifically linked to AEs in male and female patients with BC, respectively. Male‐specific AE was libido decreased (reporting odds ratio [ROR]: 43.33), and female‐specific AE was uterine disease, including sarcoma uterus (ROR: 519.51), endometrial cancer (ROR: 131.26), uterine polyp (ROR: 40.83), endometriosis (ROR: 11.39), among others. A notably higher risk of AEs in male patients with BC was observed in individuals aged >65 years (χ2 = 20.83, p < .001). Male patients with BC had a relatively higher risk of hospitalization (χ2 = 4.83, p = .03) and a lower risk of deaths (χ2 = 5.32, p = .02). Theses finding may assist healthcare professionals in recognizing the TAM‐associated AEs and understanding gender differences, potentially improving safety in clinical applications.
ConvNext Mixer‐Based Encoder Decoder Method for Nuclei Segmentation in Histopathology Images
Authors: Firat Hüseyin , Üzen Hüseyin , Hanbay Davut , Şengür Abdulkadir
Published: September 2024

Histopathology, vital in diagnosing medical conditions, especially in cancer research, relies on analyzing histopathology images (HIs). Nuclei segmentation, a key task, involves precisely identifying cell nuclei boundaries. Manual segmentation by pathologists is time‐consuming, prompting the need for robust automated methods. Challenges in segmentation arise from HI complexities, necessitating advanced techniques. Recent advancements in deep learning, particularly Convolutional Neural Networks (CNNs), have transformed nuclei segmentation. This study emphasizes feature extraction, introducing the ConvNext Mixer‐based Encoder‐Decoder (CNM‐ED) model. Unlike traditional CNN based models, the proposed CNM‐ED model enables the extraction of spatial and long context features to address the inherent complexities of histopathology images. This method leverages a multi‐path strategy using a traditional CNN architecture as well as different paths focused on obtaining customized long context features using the ConvNext Mixer block structure that combines ConvMixer and ConvNext blocks. The fusion of these diverse features in the final segmentation output enables improved accuracy and performance, surpassing existing state‐of‐the‐art segmentation models. Moreover, our multi‐level feature extraction strategy is more effective than models using self‐attention mechanisms such as SwinUnet and TransUnet, which have been frequently used in recent years. Experimental studies were conducted using five different datasets (TNBC, MoNuSeg, CoNSeP, CPM17, and CryoNuSeg) to analyze the performance of the proposed CNM‐ED model. Comparisons were made with various CNN based models in the literature using evaluation metrics such as accuracy, AJI, macro F1 score, macro intersection over union, macro precision, and macro recall. It was observed that the proposed CNM‐ED model achieved highly successful results across all metrics. Through comparisons with state‐art‐of models from the literature, the proposed CNM‐ED model stands out as a promising advancement in nuclei segmentation, addressing the intricacies of histopathological images. The model demonstrates enhanced diagnostic capabilities and holds the potential for significant progress in medical research.
Capture of live circulating tumor cells via unique surface charges from cancer patients by a novel nanotechnology
Authors: Le Wenjun , Hu Shuyuan , Zhang Pengbo , Wang Yanqi , Hu Yihui , Cui Zheng , Chen Bingdi
Published: September 2024

Circulating tumor cells (CTCs) serve as a pivotal foundation for both fundamental oncological research and the precise evaluation of therapeutic interventions. However, the isolation of CTCs from clinical blood samples presents a multitude of sophisticated challenges, predominantly associated with the specificity of biomarkers and the sensitivity of detection techniques. In our previous study, we proposed a novel detection concept for CTCs based on a signature biophysical feature on the surface of cancer cells: a negative charge regulated by glycolytic processes. In this study, we have conducted experiments to ascertain the efficacy of this proposed method in capturing CTCs from clinical blood samples of individuals afflicted with solid tumors and leukemia. Our findings indicate that the method is capable of isolating tens of thousands of viable cancer cells from various metastatic solid cancers and leukemia using a mere 1 mL of blood. These cells were enumerated using cytological imaging that identified morphological characteristics indicative of malignancy. The outcomes of our study suggest that the negatively charged surface of cancer cells is a ubiquitous trait across both cultured cancer cell lines and fresh blood samples derived from cancer patients. Moreover, the capture technology employed in this study demonstrated superior performance in comparison to antecedent methodologies, enhancing the detection and documentation of CTCs for subsequent verification and analysis. This advancement holds significant promise for the improvement of diagnostic accuracy and the monitoring of therapeutic responses in oncology.
The protective effects of esculetin against Doxorubicin‐Induced hepatotoxicity in rats: Insights into the modulation of Caspase, FOXOs, and heat shock protein pathways
Authors: Kizir Duygu , Yeşilkent Esra Nur , Öztürk Neslihan , Karağaç Medine Sibel , Isıyel Murat , Tosun Hilal , Karadaş Habibe , Ceylan Hamid , Karaman Melike , Demir Yeliz
Published: September 2024

Doxorubicin (DOX) is an anthracycline antibiotic widely employed to treat carcinoma. Nevertheless, severe cardiotoxic side effects restrict its clinical use. Esculetin, a natural flavonoid, is found abundantly in plants. This study evaluated the protective effects of esculetin against DOX‐induced hepatotoxicity in rat livers. Forty‐eight rats were randomly divided into six groups with eight rats in each group: control (I), DOX (II), esculetin (III, 50 mg/kg), esculetin (IV, 100 mg/kg), DOX+esculetin 50 (V, DOX+esculetin 50 mg/kg), and DOX+esculetin 100 (VI, DOX+esculetin 100 mg/kg). The administration of esculetin effectively mitigated alterations in the measured biochemical parameters induced by DOX. Gene expression analyses demonstrated that esculetin treatment significantly reduced the DOX‐induced expression of Foxo1, Hspa1a, Hsp4a, Hsp5a, Casp3, and Casp9 while increasing the DOX‐induced expression of Foxo3. These findings suggest that esculetin, with its antioxidant and anti‐inflammatory effects, might be a therapeutic option for protecting against DOX‐induced hepatotoxicity.
Serum Procalcitonin, Hematology Parameters, and Cell Morphology in Multiple Clinical Conditions and Sepsis
Authors: Feng Pingfeng , He Yongjian , Guan Ping , Duan Chaohui , Huang Junjie , Chai Zhixin , Wang Jingjing , Zheng Huifei , Luo Junxu , Shi Yuhuan , Li Xin , Huang Huayi
Published: September 2024

Background

The clinical value of procalcitonin (PCT) in infection diagnosis and antibiotic stewardship is still unclear. This study aimed to investigate the association between serum PCT and different clinical conditions as well as other infectious/inflammatory parameters in different septic patients in order to elucidate the value of PCT detection in infection management.

Methods

Chemiluminescence immunoassay was used for serum PCT analysis. Hematology analysis was used for complete blood cell count. Digital automated cell morphology analysis was used for blood cell morphology examination. Blood, urine, and stool cultures were performed according to routine clinical laboratory standard operating procedures. C‐reactive protein (CRP) was analyzed by immunoturbidimetry. Erythrocyte sedimentation rate test was performed using natural sedimentation methods.

Results

Outpatients, ICU patients, and patients under 2 years of age with respiratory infections had higher serum PCT levels. Septic patients had the highest‐serum PCT levels and other infection indexes. PCT levels in the blood, urine, and stool culture‐positive patients were significantly higher than in culture‐negative patients. The neutrophil granulation and reactive lymphocytes were observed together with the PCT‐level increments in different septic patients, and these alterations were lessened after treatment. There was no significant change in monocyte morphology between pre‐ and posttreatment septic patients.

Conclusions

Serum PCT is associated with neutrophil cytotoxicity and lymphocyte morphology changes in sepsis; thus, the combination of neutrophil and lymphocyte digital cell morphology evaluations with PCT detection may be a useful examination for guiding the clinical management of sepsis.
Enhancing properties of PSF membrane via a simple two‐step coating of PDA and PVP for separating oil/water emulsions
Authors: Roslan Rosyiela Azwa , Lau Woei Jye , Mohd Nawi Nadiene Salleha , Nxumalo Edward Ndumiso , Ismail Ahmad Fauzi
Published: September 2024

Background

Hydrophilic modification is a promising method to inhibit fouling formation on ultrafiltration membranes. Many relevant studies have been documented; however, most of these methods are either overly intricate or require costly chemicals, thus constraining their practical utility. In this work, we proposed a straightforward approach to modify a commercial polysulfone ultrafiltration membrane via a two‐step coating process involving polydopamine (PDA) followed by polyvinylpyrrolidone (PVP). The influences of PVP molecular weight and concentration on the surface properties of the membrane were studied for oil/water emulsion treatment.

Results

Despite the fact that the introduction of a PVP layer adversely impacted the pure water permeability of the commercial membrane, its water flux during oil/water emulsion treatment was improved due to its improved antifouling properties, which can be attributed to a lower water contact angle. It was found that increasing the PVP concentration in the coating solution could improve the water flux and oil rejection during the treatment process. This enhancement is attributed to the augmented surface hydrophilicity combined with a reduction in membrane surface pore size. Additionally, the best‐performing PVP‐modified membrane exhibited significantly higher flux recovery rate, with its value for the second and third cycles at 89.4% and 80.4%, respectively, compared to the control membrane, which recorded 80.3% and 73.9%, respectively.

Conclusion

Modifying a membrane surface with PDA/PVP coating has been proven to enhance the surface wettability and antifouling properties significantly. These modifications led to improved oil removal efficiencies, demonstrating superior performance in oil/water emulsion treatment. © 2024 Society of Chemical Industry (SCI).