bluuebunny/crossref_metadata_2025 huggingface dataset:
Rhodium‐Catalyzed Meta‐C−H Arylation of Arenes with Varied Linker Lengths: Bridging Catalytic Selectivity with Structural Diversity
Authors: Mandal Astam , Prasad Biswas Jyoti , Maiti Debabrata
Published: November 2024

The directing group (DG)‐assisted approach has so far been the major route to achieve selective C−H activation at both proximal and distal positions. While rhodium catalysts are highly effective in DG‐assisted ortho‐C−H arylation, meta‐C−H arylation with rhodium has not yet been reported. In this study, we present the first example of Rh‐catalyzed meta‐C−H arylation of arenes. We found that the 2‐cyanophenyl‐based directing group, in conjunction with arylboronic acids, selectively promotes meta‐arylation with complete mono‐selectivity. Despite significant advancements in meta‐C−H activation for substrates with shorter linkers, such as hydrocinnamic acids, benzyl alcohols/amines, etc., meta‐C−H activation of substrates with longer alkyl chains remains challenging with limited literature examples. We demonstrated that arenes with varying chain lengths, including conformationally flexible and less rigid ones such as 4‐phenylbutanoic acid, 5‐phenylvaleric acid, 6‐phenylcaproic acid, 3‐phenylpropanol, and 4‐phenylbutanol underwent meta‐arylation with high levels of regiocontrol. From a synthetic perspective, this approach could be valuable as it allows to produce biaryl derivatives of flexible arenes with native functional groups at the meta‐position. The synthetic utility of this strategy is demonstrated through the total synthesis of CNBCA, a bioactive compound possessing promising potency against the SHP2 enzyme activity in vitro.
Elucidating the Mechanism and Selectivities of Cobalt‐Catalyzed Transformation of O‐Acyl Oxime
Authors: Yu Xiaohan , Wang Yang
Published: November 2024

In this work, the mechanistic investigation on the cobalt‐catalyzed CH functionalization of O‐acyl oxime and verification of the origin of selectivities are employed using the density functional theory (DFT) method. Based on the calculations, the most energetically favorable pathway contains four steps: coordination of Co(III) species to the O‐acyl oxime, para‐selective CH activation to give a five‐membered cobaltacycle, [2,1]‐alkyne insertion, and redox‐cyclization to give the final product and regenerate the Co(III) species. IRC calculations clearly indicate that the redox‐cyclization process occurs in a concerted but highly asynchronous manner. The structural analysis reveals that the para‐CH activation occurs preferentially mainly due to the less steric hindrance. FMO analysis and energetic span model are used to disclose the origin of regioselectivity and chemoselectivity, respectively.
Preparation and Properties of Translucent Suspension Chain Polyurethane With a Broad Damping Temperature Range at Near Room Temperature
Authors: Hu Jin , Jin Sha , Hong Ling
Published: November 2024

Developing a viscoelastic polymer damping material with a broad range of effective damping temperatures at room temperature and multiple functionalities has been a prominent research focus, possessing significant economic and social importance. Herein, the elastic main chain was synthesized using branched polyester polyol (DPH) and isophorone diisocyanate (IPDI). The suspension chain prepolymer was fabricated with monohydroxy long alkyl‐chain hydroxy silicone oil (OH‐PDMS) and IPDI. Translucent and damping branched polyurethane viscoelastic materials (BPUs) were prepared by reacting the elastic main chain and the suspension chain prepolymer with the cross‐linking agent trimethylolpropane (TMP). The influences of introducing suspension chains and their content within the polyurethane structure on the damping, mechanical, dynamic mechanical, thermomechanical, and water resistance properties of the polyurethane were comprehensively investigated. The experimental results indicate that the damping factor (Tanδ
max) of polyurethane decreases from 1.17 to 0.91 with the addition of suspension chain. Then, with the increase of suspension chain content, the damping factor (Tanδ
max) decreases slightly. The damping factor (Tanδ
max) still reaches 0.84 with 66% suspension chain content. At the same time, the effective damping temperature range gradually increases from 56.4°C to 119.4°C. The glass transition temperature decreased from 58.9°C to 27.8°C, enhancing the damping performance at room temperature. It was discovered that introducing suspension chains with the SiOSi structure would delay the decomposition of soft segments and enhance heat resistance. Additionally, when the content of the suspension chain is raised to 66%, the hydrophobicity of polyurethane reaches the maximum level and the elongation at break attains 423% ± 12%.
A Fluorescent Covalent Organic Cage for Ultrafast Detection of Picric Acid and HCl Vapor Sensing
Authors: Mahto Amit Kumar , Barik Sahadev , Sarkar Moloy , Madda Jaya Prakash
Published: November 2024

Covalent organic cages (COCs) have recently gained massive attention owing to their solution processability and structural flexibility. Herein, we report an amine‐linked fluorescent COC (COC2) synthesized by adopting dynamic covalent imine chemistry followed by imine bond reduction and characterized with different spectroscopic techniques. The COC2 was utilized for highly sensitive, selective, and ultrafast detection of picric acid at the nanomolar level. The fluorescence quenching efficiency of PA towards the COC2 is 98.6 %, with a detection limit of 2.7 nM. PA sensing with the COC2, coated on a TLC plate and paper strip, exhibited an outstanding fluorescence quenching property. Furthermore, the COC2 unveiled solid‐state acidochromism upon exposure to HCl acid fumes and was transferred back to the original form on exposure to NH3 vapors.
Engineering Saccharomyces boulardii for Probiotic Supplementation of l‐Ergothioneine
Authors: Tang Chaoqun , Zhang Lu , Wang Junyi , Zou Congjia , Zhang Yalin , Yuan Jifeng
Published: November 2024

Saccharomyces boulardii, as a probiotic yeast, has shown great potential in regulating gut health and treating gastrointestinal diseases. Due to its unique antimicrobial and immune‐regulating functions, it has become a significant subject of research in the field of probiotics. In this study, we aim to enhance the antioxidant properties of S. boulardii by producing l‐ergothioneine (EGT). We first constructed a double knockout of ura3 and trp1 gene in S. boulardii to facilitate plasmid‐based expressions. To further enable effective genome editing of S. boulardii, we implemented the PiggyBac system to transpose the heterologous gene expression cassettes into the chromosomes of S. boulardii. By using enhanced green fluorescent protein (EGFP) as the reporter gene, we achieved random chromosomal integration of EGFP expression cassette. By using PiggyBac transposon system, a great variety of EGT‐producing strains was obtained, which is not possible for the conventional single target genome editing, and one best isolated top producer reached 17.50 mg/L EGT after 120 h cultivation. In summary, we have applied the PiggyBac transposon system to S. boulardii for the first time for genetic engineering. The engineered probiotic yeast S. boulardii has been endowed with new antioxidant properties and produces EGT. It has potential applications in developing novel therapeutics and dietary supplements for the prevention and treatment of gastrointestinal disorders.
Unraveling the role of counter ions in shaping the structures of helical peptides in aqueous phase
Authors: Yoon Jeseong , Jo Youngbeom , Shin Seokmin
Published: November 2024

Helical peptides, as well as proteins composed of helical peptides, play essential roles in various biological processes, including their functions as components of cell membranes and their interactions with biological membranes. Therefore, it is crucial to predict the propensity and structural characteristics of helices formed in solution or lipid environments for specific peptide sequences. Melittin and pexiganan are antimicrobial peptides (AMPs) that possess distinct sequence characteristics but exhibit similar structural properties in both solution and lipid environments. In this study, we conducted molecular dynamics simulations to investigate how the presence of counter ions creates differences in structural characteristics between these two peptides in solution. By analyzing the structures formed for each AMP using extended helical projections, we aimed to uncover the underlying principles governing the interaction between counter ions and peptide sequences, leading to the formation of stable structures. It was found that the coordination of counter ions effectively extends the helical surface and stabilizes the extended helix by reducing the electrostatic repulsion between charged residues. Our results demonstrate how sequence specificity influences helical structure formation in solution and provide an explanation for the varying degrees of synergistic effects exhibited by different helical AMPs.
Phase I study of BC001, a novel fully human immunoglobulin G1 monoclonal antibody targeting the vascular endothelial growth factor receptor‐2, in advanced solid tumors
Authors: Liu Dan , Gong Jifang , Liu Muling , Zhou Huan , Wang Shumei , Yang Jian , Shang Chenwei , Guo Xinlei , Wang Cha , Zhang Yanqiao , Shen Lin
Published: November 2024

Background

BC001 is a novel fully human immunoglobulin G1 monoclonal antibody blocking VEGFR2. This phase I study aimed to assess BC001 alone and plus chemotherapy in solid tumors.

Methods

In dose escalation part, BC001 was assessed at dose levels of 2, 4, 8, 12, 16 mg/kg on day 1,15, every 28 days, followed an accelerated titration and “3 + 3” design. BC001 plus paclitaxel was assessed at dose level of 8, 10 mg/kg. The primary endpoints included the DLT, MTD and RDE of BC001. In dose expansion part, it aimed to assess the anti‐tumor activity of BC001 alone and plus chemotherapy in gastric cancer as 2nd line treatment.

Results

Overall, 53 patients were finally enrolled in this study (phase Ia, n = 28; phase Ib, n = 25). In phase Ia part, 1 DLT (grade 4 neutropenia lasting 4 days) was observed in BC001(8 mg/kg) plus paclitaxel cohort. MTD was not reached. All patients experienced TEAEs of any grade. Twenty‐four of them suffered ≥ grade 3 TEAEs. leukopenia (n = 33, 62.3%), hemoglobin decreased (n = 32, 60.4%), neutropenia (n = 29, 54.7%) were commonly observed hematological toxicities. The half‐life of 140‐240 h. And the PK parameters were not largely influenced by combination with paclitaxel. The serum sVEGFR‐1, VEGF‐A, sVEGFR‐2 could not predict the efficacy. Based on the safety, PK and efficacy data, BC001 of 8 mg/kg was determined as RED. Among the GC patients(n = 21) who receiving BC001 plus paclitaxel as 2nd‐line treatment in phase 1b part, 6 patients achieved PR and 10 patients experienced SD. The ORR was 28.6% (95% CI 11.3%, 52.2%) and the DCR was 76.2% (95% CI 52.8%, 91.8%), with the median PFS of 5.4 months (95% CI 1.9, 7.0) and OS of 9.4 months (95% CI 5.4, NA). The median DoR was 5.1 months (95% CI 2.6, NA).

Conclusions

BC001 showed acceptable safety profile and preliminary response in both single‐agent and combination with chemotherapy cohorts, especially in GC.
Genetic Characteristics of Cutaneous, Acral, and Mucosal Melanoma in Japan
Authors: Hida Tokimasa , Idogawa Masashi , Kato Junji , Kiniwa Yukiko , Horimoto Kohei , Sato Sayuri , Sawada Masahide , Tange Shoichiro , Okura Masae , Okuyama Ryuhei , Tokino Takashi , Uhara Hisashi
Published: November 2024

Background

Acral and mucosal melanomas are more prevalent in Asians than in Caucasians, unlike cutaneous melanomas, which are predominant in Caucasians. Recent studies have suggested that non‐Caucasian cutaneous melanomas responded less to immune checkpoint inhibitors, highlighting the need for genetic profiling across ethnicities. This study aimed to elucidate the genetic characteristics of Japanese melanomas, which is an under‐researched topic.

Methods

Single‐nucleotide variants, indels, and copy number alterations in 104 Japanese melanoma patients (37 cutaneous, 52 acral, and 15 mucosal) were analyzed using custom panel sequencing.

Results

Driver events were detected in 94% of the cases. Among cutaneous melanoma cases, 76% had BRAF mutations, and 8% had NRAS mutations. In acral melanoma, BRAF (9%), NRAS (17%), KRAS (8%), KIT (19%), and NF1 (7%) mutations were detected. Major driver mutations in mucosal melanoma were detected in NRAS, KRAS, NF1, PTEN, GNAQ, and KIT. The median tumor mutational burden across all melanoma types was 4.6 mutations/Mb, with no significant difference between the cutaneous and acral/mucosal types. Of the 21 patients with both primary and metastatic lesions, 11 showed distinct mutations in each. Potentially actionable mutations were detected in 58 patients in addition to BRAF V600E/K mutations in 31.

Conclusions

This study highlights distinct genetic abnormalities and actionable alterations in Japanese melanoma patients. This suggests a lower tumor mutational burden in East Asian cutaneous melanoma, which may affect the efficacy of immune checkpoint inhibitors. The heterogeneity of driver mutations across and within individuals highlights the need for personalized treatment approaches.
Identification, In Silico Selection, and Mechanistic Investigation of Anti‐Prostatic Hyperplasia Peptides From Syngnathus schlegeli
Authors: Duan Ailing , Qu Xinjian , Lin Qiang , Qin Geng , Zhao Xiangtan , Li Si , Chen Hua , Yi Xiangxi , Wan Peng , Chen Deke , Ca Bingna , Pan Jianyu
Published: November 2024

Pipefish is traditionally used as a male tonic in China. Recent studies have shown that Syngnathus schlegeli extracts effectively combat benign prostatic hyperplasia (BPH). However, the specific active compounds involved and their mechanisms of action are not fully understood. This study aimed to investigate how pipefish peptides alleviate BPH via network pharmacology, molecular docking, and quantum chemical techniques. SN4, a gel‐separated fraction from the neutral enzymatic hydrolysates of S. schlegeli, contains 3470 peptide sequences, predominantly tetrapeptides enriched in Phe, Trp, Leu, and Ile. Network pharmacology identified SRC, AKT, and ITGB3 as primary targets. Molecular docking and in vitro tests on TP‐induced RWPE‐1 cell proliferation revealed that the peptides (FVDW and FIFE) were potentially active. In silico docking and quantum chemistry revealed that the N‐terminal Phe linked to Ile/Val in FVDW and FIFE interacted with the AKT1, ITGB3, and SRC proteins, enhancing ligand‐receptor interactions and affinity and highlighting their potential for improving BPH.
Antioxidant, Enzyme and Molecular Docking Tyrosinase Inhibitory Activities of Major Polyphenols in Boscia coriacea Graells, Grewia erythraea (Schweinf.) Chiov., Ochradenus baccatus Delile, and Orthosiphon pallidus Royle Ex Benth.
Authors: Elmi Abdirahman , Zengin Gokhan , Said Mohamed A. , Gil‐Ortiz Ricardo , Caprioli Giovanni , Piatti Diletta , Spina Rosella , Chtita Samir , Ricciutelli Massimo , Abdoul‐Latif Fatouma M. , Laurain‐Mattar Dominique
Published: November 2024

Boscia coriacea Graells (BC), Grewia erythraea (Schweinf.) Chiov. (GE), Ochradenus baccatus Delile (OB), and Orthosiphon pallidus Royle ex Benth. (OP) are medicinal plants used in Djibouti. They were evaluated to determine their total phenolic content (TPC), flavonoid content (TFC), and phytochemical profile using HPLC–MS/MS. Additionally, their antioxidant capacity was assessed through five various methods. Enzymatic activities were also measured, focusing on acetylcholinesterase (AChE), butyrylcholinesterase (BChE), α‐amylase, α‐glucosidase, and tyrosinase. OP extract had the highest TPC and exhibited the best antioxidant capacity, whereas OB and BC extracts had the highest TFC. Twenty‐seven compounds were identified and quantified by LCMS. GE extract demonstrated the highest AChE activity, whereas OP extract had the highest BChE activity. BC was most active against α‐amylase and α‐glucosidase, and only GE and OP extracts showed tyrosinase inhibition in vitro. In silico analysis, the compounds were optimized and docked to the human tyrosinase‐related protein 1 using AutoDock Vina, with absorption, distribution, metabolism, and elimination to evaluate their suitability based on key therapeutic criteria. Chlorogenic, neochlorogenic, gallic acids, and quercetin emerged as promising tyrosinase inhibitors. These plants can be a viable source in the prevention and treatment related to tyrosinase enzyme inhibition.
Percutaneous Treatment of Left Main Coronary Artery Ostial Stenosis After Bentall Operation
Authors: Çamlı Babayiğit Ezgi , Çağrı Kaya İbrahim , Özgeyik Mehmet , Turgay Yıldırım Özge
Published: November 2024

Iatrogenic coronary ostial stenosis (ICOS) is a rare but life‐threatening complication of aortic root surgery. It can occur with the incidence of 0.3%–5% and affect more commonly the left main coronary artery (LMCA) compared to the right coronary artery (RCA). Here, we present a case of non‐ST‐elevation myocardial infarction that occurred after a Bentall aortic root replacement, due to compression of the left main ostium, which was effectively treated with percutaneous coronary intervention.
Acute Stent Thrombosis Following Reprotrusion of a Calcified Nodule in the Left Main Coronary Artery
Authors: Murakami Tsukasa , Kojima Keisuke , Jinnouchi Hiroyuki , Takenoya Masanori
Published: November 2024

Calcified nodule (CN) is a high‐risk phenotype of coronary artery calcification that causes in‐stent restenosis frequently. Stent thrombosis (ST) is a critical complication following percutaneous coronary intervention, and its onset is associated with severely calcified lesions. However, the association between CN and ST remains unclear. Moreover, while reprotrusion of CNs through the stent strut is not uncommon immediately after stenting, the risk of ST associated with this acute reprotrusion of CNs is not well recognized. We present a case of a 70‐year‐old female who developed acute ST following reprotrusion of a CN in the left main coronary artery. After the successful stenting to a large CN, a prominent acute protrusion occurred, followed by the acute occlusion of the implanted stent due to massive thrombus formation. This case highlights the importance of careful monitoring for thrombus formation even after good stent expansion, especially when large acute reprotrusion of CNs is observed.
Esophagitis in a Post‐Liver Transplant Patient: A Case of Cytomegalovirus and Herpes Simplex Virus‐1 Coinfection
Authors: Chaudhary Ammad Javaid , Jamali Taher , Sohail Abdullah , Keller Christian E. , Caines Allyce , ELatrache Mazen
Published: November 2024

In post‐liver transplant patients, esophagitis presents a diagnostic and management challenge due to the potential for opportunistic infections. This case describes a 59‐year‐old female with primary sclerosing cholangitis who underwent orthotopic liver transplantation six years prior. She presented with dysphagia, and her medical history included immunosuppression with prednisone, tacrolimus, and mycophenolate and a history of achalasia treated with esophageal peroral endoscopic myotomy. Esophagogastroduodenoscopy (EGD) revealed severe esophagitis with extensive ulcerations, raising suspicion for infectious etiologies such as cytomegalovirus (CMV) and herpes simplex virus‐1 (HSV‐1). The biopsy confirmed a rare coinfection of CMV and HSV‐1, which was characterized histologically by viral cytopathic effects and immunohistochemical staining. Treatment with valganciclovir and temporary cessation of mycophenolate led to symptom resolution and viral clearance. Follow‐up EGD demonstrated healing of esophageal ulcers, with subsequent findings of Candida esophagitis but no evidence of CMV or HSV recurrence. This case highlights the importance of early endoscopic evaluation and biopsy in immunocompromised patients with esophagitis. CMV and HSV‐1 coinfection, while rare, should be considered in this population due to its association with severe complications such as perforation and bleeding. Timely antiviral therapy and immunosuppression adjustment are critical for favorable outcomes.
Rhodium‐Catalyzed Reductive Hydroformylation of Polyunsaturated Vegetable Oils Assisted by Triethylamine/N‐methylimidazole Ligands Combination
Authors: Abdallah Walid , Ferreira Michel , Becquet Chryslain , Ternel Jérémy , Bricout Hervé , Monflier Eric , Tilloy Sébastien
Published: November 2024

In this work, the reductive hydroformylation of linseed and sesame oils was carried out successfully by using a rhodium catalyst precursor associated to triethylamine/N‐methylimidazole ligands combination. Interestingly, in the presence of triethylamine and N‐methylimidazole at a precise ratio with respect to rhodium, the isomerization reaction can be inhibited and control experiments realized on methyl linoleate and methyl linolenate have clearly shown that no conjugated products were formed. This new catalytic system is full of interest since the yields in alcohols, after 24 h, are equal to 21% and 15% for Rh/triethylamine combination, whereas equal to 58% and 63% for Rh/triethylamine/N‐methylimidazole combination, for linseed and sesame oils, respectively.
Fabrication of Free‐Standing Hybrid Composite High Capacity Cathodes for Li−S Batteries with Nickel Oxide Polysulfide Adsorbent
Authors: Adalı Cem , Günsel Hilal
Published: November 2024

This study focuses on enhancing lithium‐sulfur (Li−S) battery performance by using nickel(II) oxide (NiO), as polysulfide adsorbent to mitigate the shuttle effect. Polysulfides have been shown to effectively adsorb onto the hydrophilic surfaces of polar metal oxides and thus suppress this effect. In this work, a NiO – reduced Graphene Oxide/Sulfur (NiO‐rGO/S) hybrid composite paper was developed for use as a binder‐free, flexible cathode. The characterization of the composite films was done through Fourier transform infrared spectroscopy (FT‐IR), Raman spectroscopy, thermogravimetric analysis (TG), field emission gun scanning electron microscopy (FEG‐SEM), energy dispersive x‐ray spectroscopy (EDS) and x‐ray diffraction (XRD). To test adsorption of polysulfides by NiO, ultraviolet‐visible (UV‐Vis) spectroscopy was applied. Electrochemical performance tests of CR2032 cells were also conducted by cyclic voltammetry (CV), charge‐discharge tests, electrochemical impedance spectroscopy (EIS). The NiO‐rGO/S cathode, particularly the one containing 2 % NiO, exhibited remarkable performance. It delivered an initial discharge capacity of 1230 mAh g−1, maintaining 1029 mAh g−1 after 300 cycles, with a high capacity retention of 83.1 %. This suggests that the NiO‐rGO/S hybrid composite is a promising candidate for improving the efficiency and lifespan of Li−S batteries.
A Novel Methacryloyl–Masked NIR Fluorescent Probe for Detection of Cysteine and Its Application in Bioimaging
Authors: Sonawane Prasad M. , Jain Neha , Kim JunHyuk , Jeong Park Su , Mulay Sandip V. , Balasaheb Nimse Satish , Churchill David. G.
Published: November 2024

Cysteine (Cys) detection is recognized as an essential element in this investigation due to the critical function of Cys in several physiological processes in living organisms. A new NIR fluorescent probe SNC–Cys has been synthesized by incorporating a five‐membered malononitrile derivatized ring as an electron withdrawing group, and a methacryloyl group detection moiety for cysteine. After adding Cys, SNC–Cys shows an emission of 654 nm and further works as a “Turn–on” probe via ICT photomechanism. SNC–Cys has high sensitivity and selectivity for Cys (LOD=0.46 μM) and can discriminate it from other closely related amino acids, molecules with structural similarity, and in some cases very close functional group likeness. Thus, these results allow the effective imaging of Cys in living A549 cells which indicates good cell permeability and high applicability in live cell imaging. This study anticipates that SNC–Cys could be an aid in the detection of Cys–relevant diseases.
Parts‐Per‐Million Level Loading Cyclometalated Ru(II)‐NHC Catalyzed Selective Oxidation of Olefins to Carbonyls
Authors: Konwar Monuranjan , Das Tapashi , Das Animesh
Published: November 2024

Oxidative cleavage of olefins is a useful reaction in organic synthesis. The most well‐known catalytic system is the osmium based Lemieux‐Johnson catalyst, which generally requires high catalyst loading and tends to suffer from rapid overoxidation to produce the acid predominantly. Hence, the development of a mild, general, and selective method toward the oxidative cleavage of alkenes to carbonyl compounds is highly desired. In this work, a highly efficient ruthenium‐based catalyst for olefin oxidation has been demonstrated by employing a fused π‐conjugated imidazo[1,5‐a]quinoxaline (ImQx) based NHC ligand with bidentate C(carbanion) CNHC motif. Strong C‐donor ligands, paired with a rigid backbone and ruthenium redox activity, provided exceptionally high catalytic activity and a long lifetime for olefin oxidation. Complex showed high catalytic activity and a long lifetime, TONs are several million. The catalyst tolerates numerous functional groups and can be applicable to challenging biomass, natural products, sugar, amino acids, and fatty acid‐derived substrates. Based on kinetic studies, thermodynamic activation parameters, and DFT study, the mechanistic finding demonstrated that [3+2] cycloaddition reaction is the key step in the oxidation process. The use of the by‐product NaIO3 in the catalytic efficiency has been disclosed for the first time.
Correlation Between NMR Coupling Constants and σ‐Donating Properties of N‐Heterocyclic Carbenes and Their Derivatives
Authors: Gupta Radhika , Frison Gilles
Published: November 2024

Is the 1JC−H coupling constant for protonated carbene a relevant measure of its σ‐donation ability? This paper addresses this question by comparing calculated 1JC−H values with various experimental and theoretical approaches across a broad spectrum of carbene compounds. We examined Arduengo‐type NHCs based on the 2‐imidazolylidene scaffold and many other derivatives with modified frameworks, including carbenes with extended, saturated, or conjugated rings, reduced heteroatom stabilization, alternative heteroatoms, permanently charged carbenes, acyclic carbenes, amidocarbenes, and cyclic amino(alkyl/aryl) carbenes, carbodicarbenes and carbodiphosphoranes. Our findings reveal a nuanced relationship between different parameters associated with σ‐interaction, such as 1JC−H, Huynh electronic parameter (HEP), σ‐donation from ETS‐NOCV, and lone pair energy. Notably, the best correlation was observed between 1JC−H and the ETS‐NOCV method, particularly for mono‐ and diaminocarbenes, highlighting the utility of 1JC−H in comparing σ‐donation among structurally similar carbene types. However, the use of 1JC−H as a universal measure across all carbene classes appears limited, especially when considering carbenes with significantly different structural frameworks. While HEP is less effective for carbenes with diverse structural backbones, our study suggests that 1JC−H has potential across a broader range of systems. Additionally, the analysis demonstrates that lone pair energy reflects basicity rather than σ‐donor ability.
Two‐Dimensional Janus p‐n Heterojunction of Co3O4 and CoMoO4 for Boosting Photocatalytic Oxidative Desulfurization
Authors: Wang Dongxiao , Lan Zheng , Li Yue , Huang Ying , Yin Kun , Yang Lixia , Bai Liangjiu , Wei Donglei , Yang Huawei , Chen Hou , Luo Mingchuan
Published: November 2024

Comprehensive Summary

Photocatalytic aerobic oxidative desulfurization (PAODS) is a sustainable alternative technology to traditional, energy‐intensive fuel desulfurization methods. Nonetheless, its advancement is hindered by the notable challenge of inadequate electron‐hole separation efficiency within the existing catalytic systems. Herein, a Janus 2D/2D heterostructure composed of Co3O4 and CoMoO4 is reported for the PAODS of thiophenic sulfides. Through a combination of detailed experimental characterizations and density functional theory (DFT) calculations, we elucidate the formation of a type II p‐n heterojunction in the catalyst, significantly enhancing electron‐hole separation through electric field force and reducing the possibility of electron‐hole recombination due to the spatial separation of redox centres. The photocatalyst exhibits exceptional activity and demonstrates an impressive performance of 10.4 mmol·g–1·h–1 in the oxidation of dibenzothiophene (DBT). Moreover, the photocatalyst demonstrates profound desulfurization capabilities in real diesel, reinforcing its promising prospects for industrial application. These discoveries provide invaluable insights, both scientifically and practically, towards the development of advanced photocatalysts for PAODS processes.
Tailoring Na+ Diffusion Kinetics and Structural Stability of P2‐Layered Material by W‐Lattice Doping†
Authors: Fan Hang , Xu Lei , Lei Ying , Li Jianying , Huang Tinghong , Fan Weifeng , Zhang Yun
Published: November 2024

Comprehensive Summary

The pursuit of advanced sodium‐ion batteries (SIBs) has been intensified due to the escalating demand for sustainable energy storage solutions. A W‐doped P2‐type layered cathode material, Na0.67Ni0.246W0.004Mn0.75O2 (NNWMO), has been developed to address the limitations of traditional cathode materials. Compared to the pristine Na0.67Ni0.25Mn0.75O2 (NNMO), NNWMO exhibits improved reversible capacity, excellent cycle performance, and remarkable rate performance. It can deliver an increased discharge capacity of 142.20 mAh/g at 0.1 C, with an admirable capacity retention of 80.5% after 100 cycles at high voltage. In situ XRD results demonstrate that the rivet effect related to the strong W—O bonds inhibits irreversible phase transition and enhances structural reversibility during charge/discharge processes. High‐resolution scanning transmission electron microscopy and X‐ray diffraction results confirm successful lattice doping of W6+ and increased layer spacing, contributing to favorable sodium ion diffusion kinetics. Density‐functional theory (DFT) calculation results further reveal that the smoother Na+ ion diffusion dynamics is attributed to the reduced migration energy barrier of Na+ with the insertion of W6+. This study provides valuable insights into the design of high‐performance cathode materials for next‐generation SIBs, showcasing the potential for more efficient, stable, and enduring energy storage solutions.
Commercial Blue Textile Dye Decolorization Using Aspergillus oryzae RH1 Isolated From Fermented Miso
Authors: Handersen Ricky , Wijaya Joan Christie , Victor Hans , Purnomo Jonathan Suciono , Cornelia Melanie , Kiranadi Bambang , Pakpahan Eduwin , Pinontoan Reinhard
Published: November 2024

The improper treatment of effluents from the textile industry is associated with severe health and environmental hazards. This study aimed to isolate and characterize miso‐paste fungi that can decolorize commercial blue textile dyes (identified as Reactive Violet 5 [RV5] through spectral comparison). Response surface methodology (RSM) was employed to determine the optimal decolorization conditions, whereas molecular docking was performed to propose an enzymatic degradation mechanism. One colony, displaying the typical morphological characteristics of Aspergillus oryzae common in miso‐paste starters, exhibited high decolorization potential for RV5. Validation of the RSM analysis using whole fungus A. oryzae RH1 revealed a decolorization performance of 92.33% under the following optimized conditions: 33°C, pH 6.2, dye concentration of 200 ppm, and incubation period of 6 days. The optimal conditions for dye degradation via enzymatic catalysis, with peroxidase as the enzyme, were 51°C and pH 3.0, resulting in a decolorization performance of 48.95% after 60 min of incubation. Molecular docking analysis suggested that the DyP‐type peroxidase produced by A. oryzae RH1 can oxidize the azo bond, which is the chromophore group of RV5. In addition, biosorption was found to play a significant role in the decolorization of A. oryzae RH1. Altogether, these findings lay the basis for the use of A. oryzae RH1 in bioreactor systems for textile wastewater treatment.
Changes in Emotion Regulation During the Course of Dialectical Behaviour Therapy: Effects on Non‐Suicidal Self‐Injury and Binge Eating Across Two Samples
Authors: Harris Lauren M. , Weiss Emily R. , Davis Margaret T. , Daniel Thomas Alex , Hart‐Derrick Victoria R. , Barnes Sarah , Cawood Chelsea D.
Published: November 2024

Dialectical Behaviour Therapy (DBT) has demonstrated effectiveness in reducing harmful behaviours associated with emotion dysregulation, including non‐suicidal self‐injury (NSSI) and binge eating. It has been hypothesized that the effects of DBT on NSSI and binge eating are the result of improvements in emotion regulation (ER); however, the extent to which changes in ER account for reductions in these behaviours is unclear. The present study leverages two unique clinical samples to examine the degree to which changes in ER influence changes in the frequency of NSSI and binge eating over the course of DBT. Participants included 189 Veterans receiving outpatient DBT and 117 civilians enrolled in a DBT Intensive Outpatient Program. Analyses examined changes in ER, binge eating and NSSI over the course of treatment, as well as the extent to which NSSI and binge eating frequency were influenced by changes in ER. In the Veteran sample, DBT led to improvements in ER abilities and significant reductions in NSSI and binge eating; however, changes in ER did not account for observed reductions in NSSI or binge eating. In the civilian sample, the effects of DBT on ER, NSSI and binge eating were nonsignificant. Our findings suggest that ER may not be the only mechanism through which DBT exerts its effects on NSSI and binge eating. The effects of DBT on ER and self‐damaging behaviours may vary based on factors such as treatment setting, time in treatment and clinical severity of the sample.
The Fluorescent Amyloid Ligand X34 Binding to Transthyretin (TTR) Tetramer and Fibrils: FRET and Binding Constants of a Sequential Two‐step Process
Authors: Sundnes Marikken , Swaminathan Priyanka , Lindgren Mikael , Mohite Ganesh , Hellstrand Ebba , Nyström Sofie , Hammarström Per
Published: November 2024

The amyloidogenic homotetrameric plasma protein transthyretin (TTR) has an affinity for bicyclic small molecule ligands in its two thyroxine (T4) binding sites. We have shown that native tetrameric TTR binds to amyloid ligands based on the trans‐stilbene scaffold. The fluorescent Congo‐red analogue, X34, is a symmetric bi‐trans‐stilbene that contains two salicylic acid motifs. We used fluorescence spectroscopy methods to interrogate X34 binding to the TTR tetramer and fibril. We discovered two binding sites in both TTR forms by tryptophan FRET, ligand self‐quenching, Stern‐Volmer plots and binding curves, for the latter including the competitive ligand diflunisal. X34 binds with the similar affinity as diflunisal in the first binding site (Kd1=150 nM), and negative cooperativity renders the binding to the second site with lower affinity very similar compared to diflunisal (Kd2= 1.1 μM). This behavior is coherent with the salicylic acid moiety of diflunisal binding into the binding pocket of TTR (reverse mode). Interestingly X34 binding to TTR fibrils was also well fitted to two binding sites, however with overall lower affinity (Kd1=1.2 μM; Kd2=2.1 μM) compared to binding to the native tetramer. X34 fluorescence when bound to TTR‐fibrils was significantly blue shifted compared to binding to the TTR‐tetramer.
Higher Prevalence of Tooth Loss in People With Abdominal Obesity but Normal Weight: Findings From the United States and Scottish Populations
Authors: Kang Jing , Larvin Harriet , Pavitt Sue , Wu Jianhua
Published: November 2024

Objectives

Previous research has shown that people with obesity are at a higher risk of tooth loss; however, it is unclear whether abdominal obesity (e.g., high waist circumference) is associated with tooth loss among individuals without obesity. This study aims to investigate the association between abdominal obesity and tooth loss among people who are not obese.

Material and Methods

Two cross‐sectional surveys were used: the United States' National Health and Nutrition Examination Survey (NHANES) 1999–2012 (n = 19,436) and the Scottish Health Survey (SHeS) 2008–2014 (n = 4243). Tooth loss was measured by the number of remaining teeth: 20 and over, 1–19, and edentulous. Abdominal obesity was defined by categorizing waist circumference into three levels: normal, high, and very high. Ordinal logistic regression was used to model the association between tooth loss and abdominal obesity.

Results

For people living without obesity, abdominal obesity is associated with a higher prevalence of tooth loss, and the effect is different between women and men. For women, abdominal obesity increased the chance of tooth loss by 64% (odds ratio [OR]: 1.64, 95% confidence interval [CI]: 1.16–2.34) in the NHANES and 196% (OR: 2.96, 95% CI: 1.47–5.97) in the SHeS. For men, abdominal obesity increased the chance of tooth loss by 41% (OR: 1.41, 95% CI: 1.06–1.87) in the NHANES and 65% (OR: 1.65, 95% CI: 1.02–2.73) in the SHeS.

Conclusions

This study indicated that the prevalence of tooth loss is substantially higher in people with abdominal obesity, and this association is distinctively different between men and women. These findings suggest that those who are not obese but have abdominal obesity may be an important target population for oral health prevention strategies.
Exploiting Acetal Moieties for the Synthesis of Degradable‐On‐Demand Polymeric Architectures
Authors: Romano Angela , Frattini Stefano , Miani Roberto , Gioia Claudio , Celli Annamaria , Sisti Laura
Published: November 2024

Developing polymers with labile bonds has attracted increasing attention since it can favor the chemical recycling into oligomers or even the starting monomers that could be recovered and re‐used. Different chemical bonds can break upon exposure to external stimuli, such as thermal, UV, or chemical triggers. Among these, the acetal bond can degrade under mild acidic conditions. This study focuses on the synthesis of polymers constituted by acetal moieties suitable for triggered depolymerization. In particular, the solvent‐less polyaddition of 1,4‐butanediol and 1,4‐butanediol divinyl ether was developed and optimized using a heterogeneous catalyst (Amberlyst 15) at 100 °C. The best reaction conditions in terms of catalyst loading and reagent ratio were determined through a Design‐of‐Experiment aiming to achieve high conversion, low polydispersity, and desirable molecular weight. The resulting material presented an amorphous character and thermal stability up to 220 °C. It was confirmed responsive in an acidic environment, being completely hydrolyzed in 42 days, while remaining stable at neutral and basic pH. The obtained results represent a proof of concept for the design of pH‐responsive materials through solventless, and scalable processes. The acetal moiety may be further exploited to achieve architectures presenting a sustainable end‐of‐life by implementing a recycling‐by‐design approach for new adhesives or novel degradable thermosetting materials.
On the Modeling of Inverse Memristor With Completely Explicit Memory Description: A Memorized Dielectric Relaxation Analogy‐Based Approach
Authors: Banchuin Rawid
Published: November 2024

In this work, a memorized dielectric relaxation analogy‐based model of inverse memristor has been proposed. In contrast to the previous models, a completely explicit memory description of the inverse memristor can be achieved by ours. The proposed model has been found to be well applicable to the practical inverse memristors of both current and voltage‐controlled types where the basic properties of inverse memristor have been preserved and the strong agreements between the model‐based results and their circuit‐based benchmarks can be observed. Based on our model, a rigorous analysis of inverse memristor has been performed to give a mathematical discussion on the simulation results. The power and energy consumption aspects have also been analyzed. In addition, the effect of parasitic element has been explored and it has been found that the inverse memristor realized based on our model is more robust to such undesired effect than those realized based on the others. This is another virtue of the proposed model. The realization methodology of the inverse memristor circuit based on our model with off‐the‐shelf components and the extension of the model toward the inverse memcapacitor and inverse meminductor have also been given.
Design of a Univariate Dual‐Loop Voltage System Based on the Multisampling Method
Authors: Yu Jian , Li Yanlin , Niu Aohui , Shi Zhiyuan , Hao Yulong
Published: November 2024

This study presents an innovative control framework designed for voltage source inverters (VSIs) equipped with LC output filters. The objective of this control framework is to reduce delay and suppress aliasing effects by employing multisampling techniques and implementing repetitive filtering methods. The multisampling approach can significantly reduce control delays, thereby enhancing both the bandwidth and stability margins of the system. The implementation of multisampling techniques for inverter voltage can enhance dynamic performance. However, it may introduce high‐frequency ripples in the control loop, resulting in low‐order aliasing harmonics and ultimately leading to output voltage distortion. To address this issue, a multiple notch filter with minimal phase delay is employed suppress aliasing. The optimal parameters of the system are determined by evaluating the filter specifications, filtering effectiveness, output voltage ripple, and overall system performance, while also considering the actual filtering requirements and circuit size. Its effectiveness and performance are carefully verified by experimental results.
A Distributed Mobile Edge Computing Based Dynamic Resource Allocation in 5G Network Using Green Anaconda Optimization Based Deep Learning Network
Authors: C Selvan , Govinda Rajulu G. , Padmanaban K. , Aghalya S.
Published: November 2024

Mobile edge computing (MEC) facilitates storage, cloud computing, and analysis capabilities near to the users in 5G communication systems. MEC and deep learning (DL) are combined in 5G networks to enable automated network management that provides resource allocation (RA), energy efficiency (EE), and adaptive security, thereby reducing computational costs and enhancing user services. A hybrid quantum‐classical convolutional neural network (HQCCNN) with simplicial attention network (SAN) is presented in the study that allocates appropriate resources for various users in the network. First, the green anaconda optimization (GAO) algorithm is used to optimize the objective function for effective RA. Consequently, the neural network receives the optimized objective functions to allocate resources. In the study, the suggested HQCCNN‐GAO model assesses the degree of need for every user and, based on those needs, allots resources to every user in the 5G network while preserving higher throughput and EE. Throughput, latency, mean square errors, processing time, bit error rates, and EE are used to measure the proposed model's efficiency. A few of the RA models that are now in use are contrasted with the outcomes of the suggested method. From the obtained outcomes, it is noticed that the suggested model provides a low latency of 0.08 s and a high throughput of 790 kbps for a range of network users.
Lifting the Veil of Darkness: Thermal Technology Facilitates Collection of Flight‐Initiation Distances by Night
Authors: Rendall Anthony R. , Plotz Roan D. , Yokochi Kaori , Krauss Joel , Pengelly Aaron , Di Stefano Sam A. , Swindell Sarah , Ranawana Kithsiri , Vidanapathirana Dulan R. , Weston Michael A.
Published: November 2024

Flight‐Initiation Distance (FID)—a direct measure of an individual animal's escape response—is a widely used method to study escape ecology in fauna. The technique has primarily been applied to bird species that are active by day. Indexing the escape behaviour of nocturnal species has been limited due to the need for light to detect and observe animals which confounds behavioural responses. We demonstrate the use of existing high‐end thermal technology to facilitate standardised, un‐biased, nocturnal FIDs in small and large, terrestrial and arboreal animals, which feature initial separation (starting) distances which are the same by day and night. We provide the following (1) method for collecting FIDs by night which specifically addresses solutions to novel challenges associated with collecting these by night, (2) report of the FIDs of some strictly nocturnal bird and mammal species and compare diurnal and nocturnal FIDs for some species, (3) demonstration that the positive daytime relationship between FID and Starting Distance also occurs by night, and (4) minimum sample size threshold for quantifying escape responses and how these vary when sampling the FIDs of different animal species by night. We demonstrate the capacity to conduct nocturnal FIDs on a broad range of taxa not previously studied. We recommend 25–50 samples are needed to accurately quantify a species escape response in a particular context. Our method expands the capacity to understand how species escape by night, a critical period during which many predator–prey interactions occur.
A Trade‐Off Between Leaf Carbon Economics and Plant Size Among Mangrove Species in Dongzhaigang, China
Authors: Jiang Dalong , Nie Tao , He Qiuyu , Yan Jing , Feng Erhui , Ye Qing
Published: November 2024

Plant size is closely linked to its leaf trait characteristics, which are essential for determining its form and function. These relationships constitute a fundamental component of the global spectrum of plant diversity. Despite this, the size–trait relationships in coastal mangroves have often been overlooked, with a common assumption that they would mirror those found in terrestrial tropical trees. However, recent studies have begun to challenge this assumption, revealing unique adaptations and trait variations in mangroves that are influenced by their specific environmental conditions, such as salinity and nutrient availability. In this research, we investigated the leaf structural traits, plant height, and diameter at breast height or basal height (DBH) of 10 shrub and tree species. This study was carried out along an intertidal gradient within a mangrove forest located in Southeast China. We found that leaf traits differed significantly between shrubs and trees in their response to intertidal gradients, indicating that different species have evolved specific adaptations to thrive in their respective intertidal zones. This insight can help us decipher the selective pressures that have shaped trait evolution. Among all species, leaf carbon (C) economics (leaf dry mass content, leaf mass per area, and leaf density) decreased significantly with increasing plant height and DBH. For each growth form and intertidal zone, the relationships between plant size (height or DBH) and leaf C economics traits were consistent with those in the pooled dataset. Our study reveals that mangrove plants exhibit size‐related adjustments in leaf C economic strategies, indicating that plant size potentially acts as a proxy for the “slow–fast” continuum of plant performance. This discovery is pivotal for advancing our understanding of plant functional ecology and for enhancing the precision of global C cycle models, which are highly responsive to perturbations in atmospheric CO2 and climate change.