bluuebunny/crossref_metadata_2025_split huggingface dataset:
Leveraging the Persistent Radical Effect in the Synthesis of trans‐2,3‐Diaryl Dihydrobenzofurans**
Authors: Roldan Bec J. , Hammerstad Travis A. , Galliher Matthew S. , Keylor Mitchell H. , Pratt Derek A. , Stephenson Corey R. J. 
Published: June 2023

AbstractA simple method for accessing trans‐2,3‐diaryl dihydrobenzofurans is reported. This approach leverages the equilibrium between quinone methide dimers and their persistent radicals. This equilibrium is disrupted by phenols that yield comparatively transient phenoxyl radicals, leading to cross‐coupling between the persistent and transient radicals. The resultant quinone methides with pendant phenols rapidly cyclize to form dihydrobenzofurans (DHBs). This putative biomimetic access to dihydrobenzofurans provides superb functional group tolerance and a unified approach for the synthesis of resveratrol‐based natural products.
Dynamic Kinetic Resolution of 2‐(Quinolin‐8‐yl)Benzaldehydes: Atroposelective Iridium‐Catalyzed Transfer Hydrogenative Allylation
Authors: Carmona José A. , Rodríguez‐Salamanca Patricia , Fernández Rosario , Lassaletta José M. , Hornillos Valentín 
Published: June 2023

AbstractAn atroposelective Ir‐catalyzed dynamic kinetic resolution (DKR) of 2‐(quinolin‐8‐yl)benzaldehydes/1‐naphthaldehydes by transfer hydrogenative coupling of allyl acetate is disclosed. The allylation reaction takes place with simultaneous installation of central and axial chirality, reaching high diastereoselectivities and excellent enantiomeric excesses when ortho‐cyclometalated iridium‐DM‐BINAP is used as the catalyst. The racemization of the substrates occurs through a designed transient Lewis acid‐base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group.
Tryptophan in Multicomponent Petasis Reactions for Peptide Stapling and Late‐Stage Functionalisation
Authors: Krajcovicova Sona , Spring David R. 
Published: June 2023

AbstractPeptide stapling is a robust strategy for generating enzymatically stable, macrocyclic peptides. The incorporation of biologically relevant tags (such as cell‐penetrating motifs or fluorescent dyes) into peptides, while preserving their binding interactions and enhancing their stability, is highly sought after. Despite the unique opportunities offered by tryptophan‘s indole scaffold for targeted functionalisation, its utilisation in peptide stapling has been limited as compared to other amino acids. Herein, we present an approach for peptide stapling using the tryptophan‐mediated Petasis reaction. This method enables the synthesis of both stapled and labelled peptides and is applicable to both solution and solid‐phase synthesis. Importantly, the use of the Petasis reaction in combination with tryptophan facilitates the formation of stapled peptides in a straightforward, multicomponent fashion, while circumventing the formation of undesired by‐products. Furthermore, this approach allows for efficient and diverse late‐stage peptide modifications, thereby enabling rapid production of numerous conjugates for biological and medicinal applications.
Synthesis and Reactivity of an Anionic Diazoolefin
Authors: Kooij Bastiaan , Dong Zhaowen , Fadaei‐Tirani Farzaneh , Scopelliti Rosario , Severin Kay 
Published: June 2023

AbstractBent (hetero)allenes such as carbodicarbenes and carbodiphosphoranes can act as neutral C‐donor ligands, and diverse applications in coordination chemistry have been reported. N‐Heterocyclic diazoolefins are heterocumulenes, which can function in a similar fashion as L‐type ligands. Herein, we describe the synthesis and the reactivity of an anionic diazoolefin. This compound displays distinct reactivity compared to neutral diazoolefins, as evidenced by the preparation of diazo compounds via protonation, alkylation, or silylation. The anionic diazoolefin can be employed as an ambidentate, X‐type ligand in salt metathesis reactions with metal halide complexes. Extrusion of dinitrogen was observed in a reaction with PCl(NiPr2)2, resulting in a stable phosphinocarbene.
Isocyanide Cu(I) complexes with unexpected μ2‐bridging pseudohalides: Synthesis, characterization and catalytic activity towards CuAAC
Authors: Ferraro Valentina , Sole Roberto , Álvarez‐Miguel Lucía 
Published: June 2023

Three neutral Cu(I) complexes bearing 2,6‐dimethylphenyl isocyanide (CNXyl) and different triatomic pseudohalogens (SCN−, OCN− and N3−) as ligands were efficiently synthesized and characterized. The solid‐state structures were unambiguously determined through single‐crystal X‐ray diffraction, revealing unexpected bridging coordination modes in the case of OCN− and N3−. All the complexes were tested for azide‐alkyne cycloaddition (CuAAC), showing interesting catalytic activity towards the formation of 1,4‐disubstituted‐1,2,3‐triazoles for the cyanato and the azido Cu(I) complexes. Both species afforded yields above 90% with 0.5 mol% of catalyst at 50°C for 24 h. Several alkynes and azides were tested using the more active azido Cu(I) complex, affording the corresponding triazoles in high yields. The azido Cu(I) complex also induced the intramolecular CuAAC in the presence of dimethyl acetylenedicarboxylate and benzyl bromide/phenylacetylene.
A Randomized, Double‐Blind, Sham‐Controlled, Clinical Trial of Auricular Vagus Nerve Stimulation for the Treatment of Active Rheumatoid Arthritis
Authors: Baker Matthew C. , Kavanagh Sarah , Cohen Stanley , Matsumoto Alan K. , Dikranian Ara , Tesser John , Kivitz Alan , Alataris Konstantinos , Genovese Mark C. 
Published: June 2023

ObjectivePreliminary evidence suggests that vagus nerve stimulation (VNS) may have some benefit in patients with rheumatoid arthritis (RA); however, prior studies have been small and/or uncontrolled; this study aimed to address that gap.MethodsThis randomized, double‐blind, sham‐controlled trial enrolled patients aged 18 to 75 years with active RA who had failed conventional synthetic disease‐modifying antirheumatic drugs (DMARDs) and were naïve to biologic and/or targeted synthetic DMARDs. All patients received an auricular vagus nerve stimulator and were randomized 1:1 to active stimulation or sham. The primary endpoint was the proportion of patients achieving 20% improvement in American College of Rheumatology criteria (ACR20) at week 12. Secondary endpoints included mean changes in disease activity score of 28 joints with C‐reactive protein (DAS28‐CRP) and Health Assessment Questionnaire‐Disability Index (HAQ‐DI).ResultsA total of 113 patients (mean age 54 years; 82% female) enrolled, and 101 patients (89.4%) completed week 12. ACR20 response at week 12 was 25.0% for active stimulation versus 26.9% for sham (difference vs. sham, −1.9; 95% CI, −18.8, 14.9, P = 0.823). The least square mean ± SE change in DAS28‐CRP was −0.95 ± 0.16 for active stimulation and −0.66 ± 0.16 for sham (P = 0.201); in HAQ‐DI it was −0.19 ± 0.06 for active stimulation and −0.02 ± 0.06 for sham (P = 0.044). Adverse events occurred in 17 patients (15%); all were mild or moderate.ConclusionAuricular VNS did not meaningfully improve RA disease activity. If VNS with other modalities is pursued in the future for the treatment of RA, larger, controlled studies will be needed to understand its utility.
Synovial Tissue Heterogeneity in Japanese Patients With Rheumatoid Arthritis Elucidated Using a Cell‐Type Deconvolution Approach
Authors: Nakajima Sotaro , Tsuchiya Haruka , Ota Mineto , Ogawa Megumi , Yamada Saeko , Yoshida Ryochi , Maeda Junko , Shirai Harumi , Kasai Taro , Hirose Jun , Ninagawa Keita , Fujieda Yuichiro , Iwasaki Takeshi , Aizaki Yoshimi , Kajiyama Hiroshi , Matsushita Masakazu , Kawakami Eiryo , Tamura Naoto , Mimura Toshihide , Ohmura Koichiro , Morinobu Akio , Atsumi Tatsuya , Tanaka Yoshiya , Takeuchi Tsutomu , Tanaka Sakae , Okamura Tomohisa , Fujio Keishi 
Published: June 2023

ObjectiveRecent advances in single‐cell RNA sequencing technology have improved our understanding of the immunological landscape of rheumatoid arthritis (RA). We aimed to stratify the synovium from East Asian patients with RA by immune cell compositions and gain insight into the inflammatory drivers of each synovial phenotype.MethodsSynovial tissues were obtained from East Asian patients in Japan with RA (n = 41) undergoing articular surgery. The cellular composition was quantified by a deconvolution approach using a public single‐cell–based reference. Inflammatory pathway activity was calculated by gene set variation analysis, and chromatin accessibility was evaluated using assay of transposase accessible chromatin–sequencing.ResultsWe stratified RA synovium into three distinct subtypes based on the hierarchical clustering of cellular composition data. One subtype was characterized by abundant HLA‐DRAhigh synovial fibroblasts, autoimmune‐associated B cells, GZMK+ GZMB+ CD8+ T cells, interleukin (IL)1‐β+ monocytes, and plasmablasts. In addition, tumor necrosis factor (TNF)‐α, interferons (IFNs), and IL‐6 signaling were highly activated in this subtype, and the expression of various chemokines was significantly enhanced. Moreover, we found an open chromatin region overlapping with RA risk locus rs9405192 near the IRF4 gene, suggesting the genetic background influences the development of this inflammatory synovial state. The other two subtypes were characterized by increased IFNs and IL‐6 signaling, and expression of molecules associated with degeneration, respectively.ConclusionThis study adds insights into the synovial heterogeneity in East Asian patients and shows a promising link with predominant inflammatory signals. Evaluating the site of inflammation has the potential to lead to appropriate drug selection that matches the individual pathology.
Color‐Tunable Ultralong Organic Phosphorescence: Commercially Available Triphenylmethylamine for UV‐Light Response and Anticounterfeiting
Authors: Gao Wei , Liu Zhenliang , Dai Xianyin , Sun Weitao , Gong Qi , Li Jinwei , Ge Yanqing 
Published: June 2023

AbstractDue to the unclear mechanism and lack of effective design for color‐tunable ultralong organic phosphorescence (UOP) in a single‐component molecule, the development of new types of single‐component UOP materials with color‐tunable property remains challenging. Herein, commercially available triphenylmethylamine‐based single‐component phosphors featuring color‐tunablity and ultralong lifetime (0.56 s) are reported. The changed afterglow colors from cyan to orange were observed after different wavelengths of UV excitation. Crystal structure and calculation studies show that multiple emission centers in the aggregated states may be responsible for the color‐tunablity. In addition, visual probing of UV light (from 260 to 370 nm) and colorful anti‐counterfeiting were conducted. More importantly, UV light ranging from 350 to 370 nm could be detected with the minimal interval of 2 nm. The findings provide a new type of single‐component color‐tunable UOP materials and shed new light on mechanism and design for such materials.
Pitch Carbon‐coated Ultrasmall Si Nanoparticle Lithium‐ion Battery Anodes Exhibiting Reduced Reactivity with Carbonate‐based Electrolyte
Authors: Schulze Maxwell C. , Fink Kae , Palmer Jack , Carroll Gerard M. , Dutta Nikita S. , Zwiefel Christof , Engtrakul Chaiwat , Han Sang‐Don , Neale Nathan R. , Tremolet de Villers Bertrand J. 
Published: June 2023

AbstractSilicon anodes for lithium‐ion batteries (LIBs) have the potential for higher energy density compared to conventionally used graphite‐based LIB anodes. However, silicon anodes exhibit poor cycle and calendar lifetimes due to mechanical instabilities and high chemical and electrochemical reactivity with the carbonate‐based electrolytes that are typically used in LIBs. In this work, we synthesize a pitch carbon‐coated silicon nanoparticle composite active material for LIB anodes that exhibits reduced chemical reactivity with carbonate‐based electrolytes compared to an uncoated silicon anode. Silicon primary particle sizes less than 10 nm diameter minimize micro‐scale mechanical degradation of the anode composite, while conformal coatings of pitch carbon minimize the parasitic reactions between the silicon and the electrolyte. When matched with a high voltage NMC622 (LiNi0.6Mn0.2Co0.2O2) cathode, the pitch carbon‐coated silicon anode retains ≈75 % of its initial capacity at the end of 1000 cycles. Increasing the areal loading of the pitch carbon‐coated silicon anodes to realize energy density improvements over graphite anodes results in severe mechanical degradation on the electrode level, highlighting a remaining challenge to be addressed in future work.
Ascertainment of malformations in pregnancy registries: Lessons learned in the North American AED Pregnancy Registry
Authors: Holmes Lewis B. , Quinn Moira , Conant Susan , Lyons Amy , Hauser W. Allen , Yerby Mark , Hernandez‐Diaz Sonia 
Published: June 2023

AbstractBackgroundPregnancy registries, designed to assess the safety of medications and vaccines for the exposed mother and fetus, have been developed since the 1990s. Malformations present in the exposed liveborn or stillborn infant or fetuses in elective terminations are the outcome of greatest concern. The experiences of the North American AED (antiepileptic drug) Pregnancy Registry (NAAPR) can be used to identify the challenges and limitations of a pregnancy registry in identifying congenital malformations.MethodsThe NAAPR enrolls pregnant women who are taking one or more AEDs for any medical condition, but primarily to prevent seizures, and an unexposed comparison group. Participants are interviewed by clinical research coordinators (CRCs) at enrollment, later in pregnancy and postpartum. Malformations are identified in the mother's reports and her infant's medical records through age 12 weeks. A teratologist, blinded to exposure status, evaluates each potential malformation identified.ResultsAmong 10,982 pregnancies enrolled between 1997 and 2022, 282 malformations were identified in the 9677 AED‐exposed and 15 among the 1305 unexposed infants. Isolated malformations, such as cleft palate, accounted for 84% of the malformations identified. Increased frequencies of oral clefts and myelomeningocele were associated with exposure to several different AEDs. Copies of reports from many diagnostic studies were not obtained and very few pregnancy losses had autopsies.ConclusionsThe evaluation of the AED‐exposed infants in a pregnancy registry is indirect. Improvements rely on the rapport established with the mothers by the CRCs and the mothers’ willingness to assist in obtaining information from her infants’ physicians.
Noncytotoxic Dy3+‐activated glass emits cool white light for near ultraviolet‐based white light‐emitting diodes, visible lasers, and biomedical applications
Authors: Vijayalakshmi L. , Kumar K. Naveen , Palle Kishor , Baek Jong Dae , Mohammed Abdallah A. A. 
Published: June 2023

AbstractUsing the melt quenching technique, a lithium zinc borate glass (LZB) system with trivalent dysprosium ions (Dy3+) was synthesized, and the luminescence and lasing properties of these materials were examined for the generation of white light. Structural investigation through X‐ray diffraction revealed that the prepared glass had an amorphous nature. The optimized glass containing 0.5 Dy3+ had a direct optical band gap of 2.782 eV and an indirect optical band gap of 3.110 eV. A strong excitation band at 386 nm (6H15/2→4I13/2) was recognized in the ultraviolet (UV) light region of its excitation spectrum. Emission bands could be seen in the photoluminescence spectrum at 659, 573, and 480 nm under the 386 nm excitation. These transitions of emission resembled electronic transitions such as (4F9/2→6H11/2), (4F9/2→6H13/2), and (4F9/2→6H15/2). In a pristine glass matrix, the higher intensity ratio of yellow to blue can result in the production of white light. The optimized Dy3+ ion concentration was observed to be 0.5 mol%. In addition, an analysis of lifetime decay was conducted for all synthesized glasses, and their decay trends were systematically investigated. Noticeably, we assessed the photometric parameters and found that they were close to the white light standard. Furthermore, a cytotoxicity study was carried out using lung fibroblast (WI‐38) cell lines for the optimized 0.5Dy3+‐doped LZB glass and it appeared to be noncytotoxic. It is clear from the results that the noncytotoxic LZB glass doped with 0.5 Dy3+ ions could be a suggestive choice for the manufacture of white light‐emitting diodes and lasers using near‐UVs.
Metabolic engineering of Synechococcus elongatus for photoautotrophic production of mannitol
Authors: Pritam Prem , Sarnaik Aditya P. , Wangikar Pramod P. 
Published: June 2023

AbstractWith multiple applications in food, pharmaceutical, and chemical industries as antioxidant or nonmetabolizable sweetener; the bioproduction of d‐mannitol is gaining global attention, especially with photosynthetic organisms as hosts. Considering the sustainability prospects, the current work encompasses metabolic engineering of a widely used cyanobacterial strain, Synechococcus elongatus PCC 7942, and two newly isolated fast‐growing cyanobacterial strains; S. elongatus PCC 11801 and S. elongatus PCC 11802, for mannitol production. We engineered these strains with a two‐step pathway by cloning genes for mannitol‐1‐phosphate dehydrogenase (mtlD) and mannitol‐1‐phosphatase (mlp), where the mtlD expression was under the control of different promoters from PCC 7942, namely, Prbc225, PcpcB300, PcpcBm1, PrbcLm17, and PrbcLm15. The strains were tested under the “switch conditions,” where the growth conditions were switched after the first 3 days, thereby resulting in differential promoter activity. Among the engineered strains of PCC 11801 and PCC 11802, the strains possessing Prbc225‐mtlD module produced relatively high mannitol titers of 401 ± 18 mg/L and 537 ± 18 mg/L, respectively. The highest mannitol titer of 701 ± 15 mg/L (productivity 60 mg/L.d, yield 895 µM/OD730) was exhibited by the engineered strain of PCC 7942 expressing PcpcB300‐mtlD module. It is by far the highest obtained mannitol yield from the engineered cyanobacteria.
Identification and analysis of anti‐tumor effective substances in Yangzheng Mixture
Authors: Dai Bingling , Cao Hanbing , Hu Yu , Wang Xuemei , Huang Xiaoyue , Su Xinyue , Ma Weina , Chen Yanbin , Peng Xiujuan , Gong Zhengyan , Liu Feng , Zhang Yanmin 
Published: June 2023

AbstractYangzheng Mixture is a traditional Chinese medicine used in clinical practice as an adjuvant therapy for tumors. However, little is known about its active components in tumor treatment. The purpose of this study was to explore the potential anti‐tumor components of Yangzheng Mixture to better promote its clinical application. Using LC–MS/MS, 43 components were detected in concentrated Yangzheng Mixture. Six components, comprising astragaloside, calycosin, formononetin, isoquercitrin, ononin, and calycosin‐7‐O‐β‐D‐glucoside, were identified in rat plasma. The cancer cell absorption assay showed that the intracellular concentration of four components, calycosin, calycosin‐7‐O‐β‐D‐glucoside, formononetin, and ononin, increased with extended incubation time and demonstrated potential anti‐tumor effects. The MTT assay results confirmed that Yangzheng Mixture inhibited different tumor cells proliferation. Additionally, the colony formation assay, flow cytometry analysis and wound healing displayed that Yangzheng Mixture and a combination of four components could inhibit colony formation, arrest the cell cycle and impair cell migration of tumor cells, including HCT‐116, MHCC‐97L, MCF‐7 and NCI‐H1299. In summary, our study highlighted the plausible application of Yangzheng Mixture as a potential adjuvant treatment for tumors. Furthermore, it identified effective anti‐tumor components and provided evidences for the further clinical application of Yangzheng Mixture.
Heterogeneity in corporate green supply chain practice adoption: Insights from institutional fields
Authors: Chen Yuan , Zhu Qinghua , Sarkis Joseph 
Published: June 2023

AbstractFirms adopt different green supply chain management (GSCM) practices at varying levels. Drawing on institutional field theory, this study aims to explore the heterogeneity in GSCM practice adoption considering different firm characteristics, including firm size, industry, and ownership. Secondary data from 394 firms operating in China show that four organizational groupings—brown, light brown, light green, and green—firms exist. Multinomial logistic regression results show that larger firms and firms in the electronics industry are more likely to be greener, indicating that firm size and industry play a strong role in discriminating GSCM practice adoption. Interestingly, no differences between domestic and foreign‐owned firms exist, implying that the gaps in institutional perspectives between Chinese domestic and non‐domestic ownership may be disappearing. This study provides practical implications for strategic benchmarking of GSCM practices. The results also have broader implications for firm operations within China and Chinese firms competing elsewhere.
Glutamine and amino acid metabolism as a prognostic signature and therapeutic target in endometrial cancer
Authors: Zhai Lirong , Yang Xiao , Cheng Yuan , Wang Jianliu 
Published: June 2023

AbstractIntroductionEndometrial cancer (EC) is the most common female reproductive system cancer in developed countries with growing incidence and associated mortality, which may be due to the growing prevalence of obesity. Metabolism reprogramming including glucose, amino acid, and lipid remodeling is a hallmark of tumors. Glutamine metabolism has been reported to participate in tumor proliferation and development. This study aimed to develop a glutamine metabolism‐related prognostic model for EC and explore potential targets for cancer treatment.MethodTranscriptomic data and survival outcome of EC were retrieved from The Cancer Genome Atlas (TCGA). Differentially expressed genes related to glutamine metabolism were recognized and utilized to build a prognostic model by univariate and multivariate Cox regressions. The model was confirmed in the training, testing, and the entire cohort. A nomogram combing prognostic model and clinicopathologic features was established and tested. Moreover, we explored the effect of a key metabolic enzyme, PHGDH, on the biological behavior of EC cell lines and xenograft model.ResultsFive glutamine metabolism‐related genes, including PHGDH, OTC, ASRGL1, ASNS, and NR1H4, were involved in prognostic model construction. Kaplan–Meier curve suggested that patients recognized as high risk underwent inferior outcomes. The receiver operating characteristic (ROC) curve showed the model was sufficient to predict survival. Enrichment analysis recognized DNA replication and repair dysfunction in high‐risk patients whereas immune relevance analysis revealed low immune scores in the high‐risk group. Finally, a nomogram integrating the prognostic model and clinical factors was created and verified. Further, knockdown of PHGDH showed cell growth inhibition, increasing apoptosis, and reduced migration. Promisingly, NCT‐503, a PHGDH inhibitor, significantly repressed tumor growth in vivo (p = 0.0002).ConclusionOur work established and validated a glutamine metabolism‐related prognostic model that favorably evaluates the prognosis of EC patients. DNA replication and repair may be the crucial point that linked glutamine metabolism, amino acid metabolism, and EC progression. High‐risk patients stratified by the model may not be sufficient for immune therapy. PHGDH might be a crucial target that links serine metabolism, glutamine metabolism as well as EC progression.