bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stereoselective Synthesis of 1,n‐Dicarbonyl Compounds Through Palladium‐Catalyzed Ring Opening/Isomerization of Densely Substituted Cyclopropanols
Authors: Teschers Charlotte S. , Cohen Anthony , Marek Ilan 
Published: November 2024

AbstractWe report a highly diastereoselective protocol for the synthesis of 1,4‐ and 1,5‐dicarbonyl compounds from densely substituted cyclopropanols. The methodology involves a palladium‐catalyzed ring opening reaction followed by a “metal‐walk” and oxidation of a remote hydroxyl group. The methodology represents a new application of cyclopropanols as initiation sites for chain walking remote functionalization. Importantly, this approach provides a straightforward access to highly valuable succinaldehyde derivatives bearing vicinal quaternary and tertiary stereocenters as single diastereomers.
A Microporous Hydrogen‐Bonded Organic Framework with Open Pyrene Sites Isolated by Hydrogen‐Bonded Helical Chains for Efficient Separation of Xenon and Krypton
Authors: He Lei , Li Yunbin , Li Lu , Wang Zhitao , Chen Yanting , Yuan Furong , Lan Gaoyan , Chen Chenxin , Xiang Shengchang , Chen Banglin , Zhang Zhangjing 
Published: November 2024

AbstractAchieving efficient xenon/krypton (Xe/Kr) separation in emerging hydrogen‐bonded organic frameworks (HOFs) is highly challenging because of the lack of gas‐binding sites on their pore surfaces. Herein, we report the first microporous HOF (HOF‐FJU‐168) based on hydrogen‐bonded helical chains, which prevent self‐aggregation of the pyrene core, thereby preserving open pyrene sites on the pore surfaces. Its activated form, HOF‐FJU‐168a is capable of separating Xe/Kr under ambient conditions while achieving an excellent balance between adsorption capacity and selectivity. At 296 K and 1 bar, the Xe adsorption capacity of HOF‐FJU‐168a reached 78.31 cm3/g, with an Xe/Kr IAST selectivity of 22.0; both values surpass those of currently known top‐performing HOFs. Breakthrough experiments confirmed its superior separation performance with a separation factor of 8.6 and a yield of high‐purity Kr (>99.5 %) of 184 mL/g. Furthermore HOF‐FJU‐168 exhibits excellent thermal and chemical stability, as well as renewability. Single‐crystal X‐ray diffraction and molecular modeling revealed that the unique electrostatic surface potential around the open pyrene sites creates a micro‐electric field, exerting a stronger polarizing effect on Xe than on Kr, thereby enhancing host‐Xe interactions.
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

AbstractThe 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

ABSTRACTIn 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

ABSTRACTDeveloping 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

AbstractCovalent 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

ABSTRACTSaccharomyces 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

AbstractHelical 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

AbstractBackgroundBC001 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.MethodsIn 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.ResultsOverall, 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).ConclusionsBC001 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

ABSTRACTBackgroundAcral 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.MethodsSingle‐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.ResultsDriver 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.ConclusionsThis 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

ABSTRACTPipefish 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

ABSTRACTBoscia 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

ABSTRACTIatrogenic 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

ABSTRACTCalcified 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

ABSTRACTIn 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

AbstractIn 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.