bluuebunny/crossref_metadata_2025_split huggingface dataset:
Antiaromatic Sapphyrin Isomer: Transformation into Contracted Porphyrinoids with Variable Aromaticity
Authors: Li Qizhao , Ishida Masatoshi , Wang Yunyun , Li Chengjie , Baryshnikov Glib , Zhu Bin , Sha Feng , Wu Xinyan , Ågren Hans , Furuta Hiroyuki , Xie Yongshu 
Published: November 2022

AbstractSapphyrin is a pentapyrrolic expanded porphyrin with a 22π aromatic character. Herein, we report the synthesis of a 20π antiaromatic sapphyrin isomer 1 by oxidative cyclization of a pentapyrrane precursor P5 with a terminal β‐linked pyrrole. The resulting isomer 1, containing a mis‐linked bipyrrole unit in the skeleton, exhibits a reactivity for further oxidation due to the distinct antiaromatic electronic structure, affording a fused macrocycle 2, possessing a spiro‐carbon‐containing [5.6.5.6]‐tetracyclic structure. Subsequent treatment with an acid afforded a weakly aromatic pyrrolone‐appended N‐confused corrole 3, and thermal fusion gave a [5.6.5.7]‐tetracyclic‐ring‐embedded 14π aromatic triphyrin(2.1.1) analog 4. The cyclization at the mis‐linked pyrrole moiety of P5 played a crucial role in synthesizing the antiaromatic porphyrinoid susceptible to facile transformation to novel porphyrinoids with variable aromaticity.
Rhodium‐Catalyzed Anti‐Markovnikov Transfer Hydroiodination of Terminal Alkynes**
Authors: Boehm Philip , Kehl Niklas , Morandi Bill 
Published: November 2022

AbstractA rhodium‐catalyzed anti‐Markovnikov hydroiodination of aromatic and aliphatic terminal alkynes is reported. Depending on the choice of ligand and substrate, either (E)‐ or (Z)‐configured alkenyl iodides are obtained in high to exclusive isomeric purity. The reaction exhibits a broad substrate scope and high functional group tolerance, employing easily accessible or commercially available aliphatic iodides as HI surrogates through a shuttle process. The synthesized vinyl iodides were applied in several C−C and C−heteroatom bond‐forming reactions with full retention of the stereoselectivity. The developed method could be used to significantly shorten the total synthesis of a marine cis‐fatty acid. Additionally, initial deuterium‐labeling experiments and stoichiometric reactions shed some light on the potential reaction mechanism.
CO2 Induces Symmetry Breaking in Layered Dipeptide Crystals
Authors: Li Xianbao , Li Qi , Wu Aoli , Li Junbai 
Published: November 2022

AbstractControl of symmetry breaking of materials provides large opportunities to regulate their properties and functions. Herein, we report breaking the symmetry of layered dipeptide crystals by utilizing CO2 to induce the adjacent monomolecular layers to stack from the opposite to the same direction. The role of CO2 is to cover the interlayer interaction sites and force the dipeptides to adsorb at asymmetric positions. Further, the dipeptide crystals exhibit far superior piezoelectricity after symmetry breaking and the piezoelectric voltage generated from the dipeptide‐based generators becomes more than 500 % higher than before. This work reveals a potential route to engineer structures and properties of layered materials and provides a deep insight into the control of non‐covalent interactions.
In Vivo Biocatalytic Cascades Featuring an Artificial‐Enzyme‐Catalysed New‐to‐Nature Reaction**
Authors: Ofori Atta Linda , Zhou Zhi , Roelfes Gerard 
Published: November 2022

AbstractArtificial enzymes utilizing the genetically encoded non‐proteinogenic amino acid p‐aminophenylalanine (pAF) as a catalytic residue are able to react with carbonyl compounds through an iminium ion mechanism to promote reactions that have no equivalent in nature. Herein, we report an in vivo biocatalytic cascade that is augmented with such an artificial enzyme‐catalysed new‐to‐nature reaction. The artificial enzyme in this study is a pAF‐containing evolved variant of the lactococcal multidrug‐resistance regulator, designated LmrR_V15pAF_RMH, which efficiently converts benzaldehyde derivatives produced in vivo into the corresponding hydrazone products inside E. coli cells. These in vivo biocatalytic cascades comprising an artificial‐enzyme‐catalysed reaction are an important step towards achieving a hybrid metabolism.
Analysis of periodic magnetohydrodynamics effects on triple diffusive nonlinear mixed convective flow of Eyring–Powell nanoliquid
Authors: Patil Prabhugouda Mallangouda , Kulkarni Madhavarao 
Published: November 2022

AbstractThe article spotlights aspects of the triply diffusive mixed convective flow of Eyring–Powell nanoliquid over a vertical plate. A periodic magnetic field with nonlinear convection is exhibited. The governing partial differential equations (PDEs) with boundary restrictions are the case paradigm transformed into a non‐dimensional system by feasible non‐similar transformations. The quasilinearization technique combined with an implicit finite difference scheme is used for numerical simulation, resulting in a block‐tridiagonal matrix form. Furthermore, a system of algebraic linear equations has been solved through Varga's algorithm. The numerical outcomes are correlated with various physical parameters graphically. The variations in the nonlinear mixed convection parameter and Powell–Eyring liquid parameter raise the skin friction coefficient more than a Newtonian fluid. In a periodic magnetic field, the fluid temperature rises and drops in the corresponding energy transfer rate. Also, wavy variations have been observed because of oscillatory magnetic fields. The current study can find its potential applications in medical, engineering and industrial developments, including polymer sheet manufacture, medicine cover coating, fibre production, crystal growth, heat exchangers and metal extrusion.
Modeling the evolution of graphene agglomeration and the electrical and mechanical properties of graphene/polypropylene nanocomposites
Authors: Du Han , Zhang Juanjuan , Fang Chao , Weng George J. 
Published: November 2022

AbstractGraphene agglomeration tends to develop with the increase of graphene loading. In this article, we present a unified model that first considers the evolution of graphene agglomeration and then incorporates it into the calculation of electrical and mechanical properties of agglomerated graphene/polymer nanocomposites. In the evolution of graphene agglomerates, a modified nanoparticle distance in terms of yield strength is introduced, while in the calculation of composite properties, a two‐scale framework that consists of the graphene‐rich agglomerates and the remainder as the graphene‐poor region is constructed. In electrical conduction, electron tunneling is modeled through Simmons formula and its difference with the widely used Cauchy function is compared. We highlight that both Simmons and Cauchy functions could well describe the interfacial tunneling activity, but the former is physics‐based while the latter is statistics‐based. In the calculation of nonlinear elastoplastic response, a field‐fluctuation method is adopted. We also demonstrated how the presented model gives rise to experimentally consistent electrical and mechanical properties of graphene/polypropylene nanocomposites, and how filler agglomeration hinders the performance of the materials.
Highly selective adsorption of Pt(IV) from spent catalyst by polyethyleneimine functionalized polyethylene/polypropylene non‐woven fabric
Authors: Feng Xinxin , He Yulong , Xing Zhe , Zhang Mingxing , Li Rong , Wu Guozhong 
Published: November 2022

AbstractAiming at efficient recovery of platinum (Pt) from aqueous solution, the aminated polyethylene/polypropylene non‐woven fabric (PE/PP NWF) was synthesized via radiation grafting of glycidyl methacrylate (GMA), followed by ring‐opening reaction with polyethyleneimine (PEI). The effects of different parameters, including pH, sorption time, initial Pt(IV) concentration, competing ions and adsorbent dosage on the Pt(IV) adsorption performance were investigated by batch adsorption tests. A high Pt(IV) adsorption capacity of 485.0 mg g−1 (initial concentration: 263.5 mg L−1) was achieved, and the adsorption kinetics and isotherm conformed to the pseudo‐second‐order model and the Langmuir isotherm model, respectively. Moreover, the PEI functionalized PE/PP NWF exhibited excellent adsorption performance over the wide pH range (1–6), and also good selectivity for Pt(IV) over multiple coexisting metal cations (Ni, Cu, Co, Pb, Mg, and Zn). The recovery ratio of Pt from spent proton exchange membrane fuel cell (PEMFC) catalysts reached 89.7% after three cycles of regeneration.
Discovery of novel pyrazole and pyrazolo[1,5‐a]pyrimidine derivatives as cyclooxygenase inhibitors (COX‐1 and COX‐2) using molecular modeling simulation
Authors: Ayman Radwa , Radwan A. M. , Elmetwally Amira M. , Ammar Yousry A. , Ragab Ahmed 
Published: November 2022

AbstractSearching for effective and selective anti‐inflammatory agents, our study involved designing and synthesizing new pyrazole and pyrazolo[1,5‐a]pyrimidine derivatives 4–11. The structures of the synthesized derivatives were confirmed using different spectroscopic techniques. Virtual screening was achieved for the newly designed derivatives using in silico docking simulation inside the active sites of four proteins classified as two cyclooxygenases (COX)‐1 (PDB: 3KK6 and 4OIZ) and two COX‐2 (PBD: 1CX2 and 3LN1). Among them, six derivatives 4c, 5b, 6a, 7a, 7b, and 10b displayed the highest binding energy. These derivatives were evaluated for their in vitro COX‐1 and COX‐2 inhibitory activities and their selectivity indexes were calculated. Additionally, these derivatives displayed IC50 values ranging between 4.909 ± 0.25 and 57.53 ± 2.91 µM, and 3.289 ± 0.14 and 124 ± 5.32 µM, against COX‐1 and COX‐2, respectively. Furthermore, the tested derivatives were found to have selective inhibitory activity on the COX‐2 enzyme. Surprisingly, the two pyrazole derivatives 4c and 5b were found to be the most active, with IC50 values of 9.835 ± 0.50 and 4.909 ± 0.25 µM and 4.597 ± 0.20 and 3.289 ±  0.14 µM compared with meloxicam (1.879 ± 0.1 and 5.409 ±  0.23 µM) and celecoxib (5.439 ± 0.28 and 2.164 ± 0.09 µM) against COX‐1/‐2, respectively. Besides, two pyrazole derivatives, 4c and 5b, displayed a COX‐1/COX‐2 SI of 2.14 and 1.49. Computational techniques such as molecular docking, density function theory (DFT) calculation, and chemical absorption, distribution, metabolism, excretion, and toxicity evaluation were applied to explain the molecules’ binding mode, chemical nature, drug likeness, and toxicity prediction.
Measurement invariance of the Autism Impact Measure (AIM) across sex in children with autism spectrum disorder
Authors: Zhong Nicole H. , Grimm Ryan P. , Kanne Stephen M. , Mazurek Micah O. 
Published: November 2022

AbstractMeasurement invariance, or the degree to which an instrument measures constructs consistently across subgroups, is critical for appropriate interpretations of measures. Given sex differences in the phenotypic and clinical presentation of autism spectrum disorder (ASD), it is particularly important to examine measurement invariance in autism instruments to ensure that ASD measures are not biased toward the more common male ASD phenotype. This study represents an important preliminary investigation evaluating the measurement equivalence of the Autism Impact Measure (AIM) across children and adolescents with ASD. The results indicated that the AIM demonstrated measurement invariance at the configural, metric, and scalar levels across sex in all five domains, including Repetitive Behavior, Communication, Atypical Behavior, Social Reciprocity, and Peer Interaction. These results suggest that ASD core symptoms assessed by the AIM were similar among male and female groups. In addition, the latent means for all five factors were not statistically significantly different across sex groups, revealing no systematic differences on any of the AIM subscales for males and females. Overall, this study showed that the AIM detects core ASD symptoms across all five areas equivalently in males and females and is not biased toward males with ASD.
Embryo‐fetal developmental toxicity and toxicokinetics of loxoprofen tromethamine intravenously administered to pregnant rats
Authors: Yue Peng , Zhao Xinxin , Lu Fan , Gao Qingfa , Qiao Hongqun , Liu Jing 
Published: November 2022

AbstractBackgroundLoxoprofen tromethamine is a novel structural compound related to loxoprofen. It has been used for the treatment of pain and inflammation. However, the embryo‐fetal developmental toxicity (EFDT) of loxoprofen tromethamine has not been evaluated in detail in vivo. This study investigated the EFDT and toxicokinetics of loxoprofen tromethamine in rats.MethodsThe aim of this study was to investigate the potential reproductive toxicity on embryo‐fetal development of loxoprofen tromethamine (0, 1, 3, and 10 mg/kg/day) and sodium cyclophosphamide (CP) (2.8 mg/kg/day) administered by intravenous injection to pregnant rats during gestation days (GDs) 6–15. Pregnant rats were euthanized on GD20. The numbers of live/dead fetuses, resorptions, implantations, and corpora lutea, gravid uterus mass, placenta mass, fetal gender ratios, body weight, and skeletal development were evaluated. In a concomitant toxicokinetic (TK) study (10 pregnant rats per group), plasma TK parameters and the tissue distribution of loxoprofen tromethamine were tested.ResultsOn GD20, rats were anesthetized and dissected by caesarean section. The appearance, internal organs, gravid uterus weight, embryo implantation number, and implantation loss rate in maternal rats of each group did not reveal any lesions. In fetuses, there were no significant differences in the fetus weight, embryo resorption number, stillbirth number, or fetal visceral examination in all test groups compared to the negative control group. However, in the high‐dose group, the fetuses showed significant differences in the anomalies of the bones compared to the negative control group. The TK study showed that in the dose range of 1–10 mg/kg, the Cmax and AUC(0–t) of loxoprofen tromethamine in animals after the first administration increased proportionally to the dose, showing linear kinetic characteristics; after the last administration, the Cmax and AUC(0–t) increased disproportionately to the dose, showing nonlinear kinetic characteristics. The results of tissue distribution show that loxoprofen tromethamine was mainly distributed in the placenta and lung after the intravenous administration to pregnant rats; the content in the liver was lower and increased sharply in the heart with increasing doses; the content in all tissues was lower than that in the plasma. Loxoprofen tromethamine in fetal tissues and organs was mainly distributed in fetal lungs, liver and heart, and the lowest content was in amniotic fluid.ConclusionsIn conclusion, the no‐observed‐adverse‐effect level (NOAEL) and lowest‐observed‐adverse‐effect level (LOAEL) of loxoprofen tromethamine were considered to be 1 and 10 mg/kg/day, respectively.
Proteomic profiling of intestinal epithelial‐like cell‐derived exosomes regulated by epigallocatechin gallate
Authors: Yano Satoshi , Suzuki Katsuhiko , Hara Taichi 
Published: November 2022

AbstractExosomes are extracellular vesicles primarily responsible for intercellular communication, and they contain nucleic acids and proteins. Exosome secretion has been observed in the intestines, suggesting their physiological effects on the receptor cells of target tissues. It is possible that intestinal epithelial cells recognize food components as ligands, resulting in exosome secretion. However, research on intestine‐derived exosomes regulated by food ingredients is limited. In this study, Caco‐2 cells were utilized as an intestinal epithelial model for proteomic profiling. NanoLC‐MS/MS analysis revealed the alteration of exosome properties by epigallocatechin gallate (EGCG) in differentiated Caco‐2 cells. This natural polyphenol reduced both the number and size of secreted exosomes and altered the expression of exosomal proteins. The enriched proteins in exosomes were involved in immune response and cell proliferation. In contrast, those in the EGCG‐treated group had distinctive functions in the maintenance of skin homeostasis. We also found variable expression of galectin‐3‐binding protein and fibronectin as molecular signatures in exosomes derived from EGCG‐treated cells. These results could help elucidate the expression and mechanism of exosomal proteins related to food components.
Face painting as an anatomical learning tool based on individual ultrasonographic examination
Authors: Hu Hyewon , Piao Jiong‐Zhen , Lee Ji‐Hyun , Bae Hyungkyu , Choi You‐Jin , Hong Sung Ok , Gil Young‐Chun , Hu Kyung‐Seok , Kim Hee‐Jin 
Published: November 2022

AbstractConsidering the shift to online education during the COVID‐19 pandemic, new and easily accessible educational videos and content on clinical anatomy are necessary. This study utilized numerous references and data on the anatomy of Asian facial muscles and blood vessels to accurately depict human anatomy through face painting. It aimed to provide clinicians accurate educational video content on anatomy to help prevent possible complications during noninvasive facial and surgical procedures. A 26‐year‐old Korean‐Chinese male volunteer was used as a face painting model. The location of the blood vessels of the face was confirmed through ultrasonography images using a real‐time two‐dimensional B‐mode. The model's face was painted by an artist majoring in anatomy. To reveal most anatomical structures on both sides of the face, the left side showed the structures observed when the skin and superficial fat layer are removed, and the right side revealed the deeper layer structures that can be seen when some muscles are cut. Fifteen superficial and deep muscles important in esthetic procedures were meticulously painted on the face. The face painting took a total of 6 h, and the video was edited to 5 min. This study merged the advantages of 2D and 3D by painting directly on the skin surface of a living model. Thus, it can provide more dynamic surface anatomy data. These contents inform clinicians about 3D anatomic location, which can help avoid complications when performing clinical procedures on the face.
The rational application of liquid biopsy based on next‐generation sequencing in advanced non‐small cell lung cancer
Authors: Zhao Chenglong , Li Jianghua , Zhang Yongchang , Han Rui , Wang Yubo , Li Li , Zhang Yimin , Zhu Mengxiao , Zheng Jie , Du Haiwei , Hu Chen , Zhou Chengzhi , Yang Nong , Cai Shangli , He Yong 
Published: November 2022

AbstractBackgroundPlasma and tissue biopsy have both used for targeting actionable driver gene mutations in lung cancer, whose concordance is imperfect. A reliable method to predict the concordance is urgently needed to ease clinical application.MethodsA total of 1012 plasma samples, including 519 with paired‐tissue biopsy samples, derived from lung adenocarcinoma patients were retrospectively enrolled. We assessed the associations of several clinicopathological characteristics and serum tumor markers with the concordance between plasma and tissue biopsies.ResultsWhen carcinoembryonic antigen (CEA) levels were higher than thresholds of 15.01 ng/ml and 51.15 ng/ml, the positive predictive value of concordance reached 90% and 95%, respectively. When CEA levels were lower than thresholds of 5.19 ng/ml and 3.26 ng/mL, the negative predictive value of concordance reached 45% and 50%. The performance of CYFRA21‐1 in predicting concordance was similar but inferior to CEA (AUC: 0.727 vs. 0.741, p = 0.633). The performance of CEA combined with CYFRA21‐1 in predicting the concordance was similar to that of the combination of independent factors derived from the LASSO regression model (AUC: 0.796 vs. 0.818, p = 0.067). CEA (r = 0.47, p < 0.01) and CYFRA21‐1 levels (r = 0.45, p < 0.05) were significantly correlated with the maximum variant allele frequency, respectively.ConclusionsCEA combined with CYFRA21‐1 could effectively predict the concordance between plasma and tissue biopsies, which could be used for evaluating the priority of plasma and tissue biopsies for gene testing to timely guide clinical applications in advanced lung adenocarcinoma patients.
Perioperative treatment and biomarker analysis of LP002, an anti‐PD‐L1 antibody, plus chemotherapy in resectable gastric and gastroesophageal junction cancer
Authors: Tang Jia‐lin , Zhang Bo , Xu Jian‐ping , Qi Ling , Xin Dao , Wang Lin , Wang Bing‐zhi , Tian Yan‐tao , Li Yong , Huang Jing 
Published: November 2022

AbstractBackgroundThe addition of immune checkpoint inhibitors to perioperative chemotherapy in operable gastric or gastroesophageal junction (GEJ) cancer has become one of the research hotspots, while reliable biomarkers for efficacy are lacking. We conducted a phase 1 trial to assess the safety and efficacy of LP002, an anti‐PD‐L1 antibody, plus chemotherapy as perioperative treatment in patients with gastric or GEJ cancer.MethodsWe enrolled patients with resectable and PD‐L1 positive gastric or GEJ cancers. Eligible patients received three preoperative and six postoperative cycles of intravenous LP002 with cisplatin and 5‐fluorouracil, repeated every 2 weeks. The primary endpoint was safety. Secondary endpoints included rate of margin‐free (R0) resection and pathological complete response (pCR). We also characterized changes in the tumor immune microenvironment using multiplex immunofluorescence (MIF) staining and next‐generation sequencing (NGS) with pre‐ and post‐treatment tumor samples.ResultsThirty patients were enrolled, of whom 28 had GEJ cancer. With a median follow‐up of 7.9 months, all patients completed preoperative treatment, and 27 patients underwent surgery. Twenty‐four patients underwent R0 resection. Six patients (20.0%) had Mandard tumor regression grade (TRG) 1–3, including one achieving pCR. Twenty‐seven patients had treatment‐related adverse events (TRAEs), while grade 3–4 TRAEs were observed in 11 patients. No treatment‐related deaths occurred. MIF staining revealed that TRG 1–3 group was associated with a higher density of PD‐L1+/CD68+ cells in the pre‐treatment tumor parenchyma than TRG 4–5 group (p = 0.048). NGS studies with paired pre‐ and post‐treatment tumor samples revealed the disappearance of pre‐existing mutations, the emergence of new mutations, and variations in the abundance of mutations after preoperative LP002 and chemotherapy. Meanwhile, tumor mutational burden decreased in patients with TRG 1–3 (p = 0.0313).ConclusionsLP002 plus cisplatin and 5‐fluorouracil are safe in patients with gastric or GEJ cancer, and patient selection via appropriate biomarkers is needed in the future.