bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photochemical Deracemization of 3‐Substituted Oxindoles
Authors: Großkopf Johannes , Heidecker Alexandra A. , Bach Thorsten 
Published: May 2023

AbstractRacemic 3‐substituted oxindoles were successfully converted into enantiomerically pure or enriched material (up to 99 % ee) upon irradiation at λ=366 nm in the presence of a chiral benzophenone catalyst (10 mol %). The photochemical deracemization process allows predictable editing of the stereogenic center at carbon atom C3. Light energy compensates for the associated loss of entropy and enables the decoupling of potentially reversible reactions, i.e. a hydrogen atom transfer to (photochemical) and from (thermal) the carbonyl group of the catalyst. The major enantiomer is continuously enriched in several catalytic cycles. The obtained oxindoles were shown to be valuable intermediates for further transformations, which proceeded with complete retention at the stereogenic center.
Modular Oxime Formation by a trans‐AT Polyketide Synthase
Authors: Minas Hannah A. , François Romain M. M. , Hemmerling Franziska , Fraley Amy E. , Dieterich Cora L. , Rüdisser Simon H. , Meoded Roy A. , Collin Sabrina , Weissman Kira J. , Gruez Arnaud , Piel Jörn 
Published: May 2023

AbstractModular trans‐acyltransferase polyketide synthases (trans‐AT PKSs) are enzymatic assembly lines that biosynthesize complex polyketide natural products. Relative to their better studied cis‐AT counterparts, the trans‐AT PKSs introduce remarkable chemical diversity into their polyketide products. A notable example is the lobatamide A PKS, which incorporates a methylated oxime. Here we demonstrate biochemically that this functionality is installed on‐line by an unusual oxygenase‐containing bimodule. Furthermore, analysis of the oxygenase crystal structure coupled with site‐directed mutagenesis allows us to propose a model for catalysis, as well as identifying key protein‐protein interactions that support this chemistry. Overall, our work adds oxime‐forming machinery to the biomolecular toolbox available for trans‐AT PKS engineering, opening the way to introducing such masked aldehyde functionalities into diverse polyketides.
Alkali Chloride Adducts of Acyclic Acylaluminum: Synthesis, Structure, and Reactivity Studies
Authors: Feng Genfeng , Yamashita Makoto 
Published: May 2023

AbstractTwo acyclic acylaluminums and one cyclic acylaluminum dimer were synthesized by reaction of the recently reported Al‐anion with acyl chloride. The reaction of the acylaluminums with TMSOTf and DMAP gave a ring‐expanded iminium‐substituted aluminate and a 2‐C−H cleaved product. In the reaction of acylaluminums toward C=O and C=N bonds, acyclic acylaluminums reacted as an acyl nucleophile, while the cycilc dimer showed no reactivity. Amide‐bond forming ligation using acyclic acylaluminums and hydroxylamines was further demonstrated. Throughout the study, acyclic acylaluminums exhibited higher reactivity than that of the cyclic dimer.
Phase‐Engineered Robust Cocatalyst of NiFe Bicarbonate with Pt Dopant for Enhanced Photocatalytic Water Splitting
Authors: Shao Mengmeng , Fu Shushu , Cao Yongyong , Hao Shiji , Dang Haifeng , Chen Min , Jin Jutao , Wang Wenlong , Wang Jiaxing , Zuo Lina , Zhang Dexing , Wang Xiaoji 
Published: May 2023

AbstractExploring efficient cocatalysts capable of accelerating surface catalytic reaction is of great significance for the development of solar‐driven hydrogen production. Herein, on the basis of NiFe hydroxide, we developed a series of Pt doped NiFe‐based cocatalysts to promote the photocatalytic hydrogen production of graphitic carbon nitride (g‐C3N4). We find that the Pt doping can trigger phase reconstruction of NiFe hydroxide and lead to the formation of NiFe bicarbonate, which displays higher catalytic activity toward hydrogen evolution reaction (HER). The Pt doped NiFe bicarbonate modified g‐C3N4 shows excellent photocatalytic activity with H2 evolution rate up to 100 μmol/h, which is more than 300 times that of pristine g‐C3N4. The experimental and calculation results demonstrate that the greatly improved photocatalytic HER activity of g‐C3N4 is not only due to the efficient carrier separation, but also attributed to the accelerated HER kinetics. Our work may provide guidance for designing novel and superior photocatalysts.
Autism severity level affects working memory and planning but not inhibition, shifting and emotional control
Authors: Memisevic Haris , Pasalic Arnela , Saletovic Amra 
Published: May 2023

AbstractAutistic children often have difficulties in executive functions (EF). These difficulties can, in turn, affect their everyday functioning. It is less clear in what way EF are affected by the severity of autism symptoms in children. We hypothesize that autism severity level does not have the same effect across the different components of EF. In this study, we examined how EF are affected by the autism severity level in a sample of 52 autistic children aged 4–7 years (mean age‐ 5.4 years, SD‐ 0.9 years). EF were measured through teachers' reports on the Behavior Rating Inventory of Executive Functions‐ Preschool Version. Autism severity level was measured with the Social Communication Questionnaire‐ Current Form. The results of this study showed that autism severity level impacted two EF, namely Planning and Working memory, and did not affect three EF components: Inhibition, Shifting, and Emotional Control. These results indicate that the cool or cognitive EF are more affected by autism severity level than hot EF. We conclude the article with suggestions for improving EF in autistic children.
Characteristics and clinical outcomes in young‐onset cholangiocarcinoma
Authors: Reddy Sarah , Goksu Suleyman Yasin , Sanford Nina N. , Kainthla Radhika , Hsiehchen David , Sanjeevaiah Aravind , Jones Amy L. , Karagkounis Georgios , Al Mutar Salwan , Ahn Chul , Beg Muhammad S. , Kazmi Syed M. 
Published: May 2023

AbstractBackgroundWhile the incidence of cholangiocarcinoma is rising, little is known about young‐onset disease. We compared clinical characteristics and outcomes between patients with young‐onset cholangiocarcinoma, diagnosed between the ages of 18 and <50 years, and patients with typical‐onset cholangiocarcinoma, diagnosed at age 50 years or greater.MethodsWe used the National Cancer Database to identify patients with young‐onset cholangiocarcinoma (n = 2520) and typical‐onset cholangiocarcinoma (n = 23,826). We compared the frequency of demographic and clinical characteristics between the two groups. We compared overall survival between the two groups using multivariable Cox regression analysis after adjusting for age, gender, race/ethnicity, comorbidity, facility type, tumor location, tumor stage, surgical status, and receipt of radiotherapy, chemotherapy and surgery.ResultsWhen compared to patients with typical‐onset disease (median age 68 years), patients with young‐onset cholangiocarcinoma (median age 44 years) were more likely to be non‐White (35.0% vs. 27.4%, p < 0.01), and had lower overall comorbidity burden. Patients with young‐onset disease had a greater proportion of intrahepatic cholangiocarcinoma (56.0% vs. 45.5%, p < 0.001) and stage IV disease (50.5% vs. 43.5%, p < 0.001). Younger patients were more likely than typical‐onset patients to receive definitive surgery (30.9% vs. 25.0%, p < 0.001), radiation (27.7% vs. 19.6%, p < 0.001) and chemotherapy (73.1% vs. 50.1%, p < 0.001). In adjusted analyses, patients with young‐onset disease had a 15% decreased risk of death, compared with patients with typical‐onset disease (HR 0.85 [95% CI 0.80–0.89], p < 0.001).ConclusionsPatients with young‐onset cholangiocarcinoma may represent a demographically and clinically distinct group from those with more typical‐onset disease.
Plasma cell myeloma with RAS/BRAF mutations is frequently associated with a complex karyotype, advanced stage disease, and poorer prognosis
Authors: Li Nianyi , Lin Pei , Zuo Zhuang , You M. James , Shuai Wen , Orlowski Robert , Manasanch Elisabet E. , Li Shaoying , Xu Jie , Garces Sofia , Jelloul Fatima Zahra , Tang Zhenya , Wang Wei , Medeiros L. Jeffrey , Yin C. Cameron 
Published: May 2023

AbstractBACKGROUNDMutations in the RAS‐MAPK pathway, such as KRAS, NRAS, and BRAF, are known as high‐risk factors associated with poor prognosis in patients with various cancers, but studies in myeloma have yielded mixed results.METHODSWe describe the clinicopathologic, cytogenetic, molecular features, and outcomes of 68 patients with RAS/BRAF‐mutated myeloma, and compare with 79 patients without any mutations.RESULTSWe show that KRAS, NRAS, and BRAF were mutated in 16%, 11%, and 5% of cases, respectively. RAS/BRAF‐mutated patients had lower hemoglobin and platelet counts, higher levels of serum lactate dehydrogenase and calcium, higher percentage of bone marrow plasma cells, and more advanced R‐ISS stage. RAS/BRAF mutations were associated with complex karyotype and gain/amplification of CKS1B. The median overall survival and progression‐free survival were significantly shorter for RAS/BRAF‐mutated patients (69.0 vs. 220.7 months, p = 0.0023 and 46.0 vs. 60.6 months, p = 0.0311, respectively). Univariate analysis revealed that KRAS mutation, NRAS mutation, lower hemoglobin, elevated lactate dehydrogenase, higher R‐ISS stage, complex karyotype, gain/amplification of CKS1B, monosomy 13/RB1 deletion and lack of autologous stem cell transplantation were associated with poorer prognosis. Multivariate analysis showed that KRAS mutation, lower hemoglobin level, higher level of serum calcium, higher ISS stage, and lack of autologous stem cell transplantation predict inferior outcome.CONCLUSIONSRAS/BRAF mutations occur in 30%–40% of myeloma cases and are associated with higher tumor burden, higher R‐ISS stage, complex karyotype, and shorter overall survival and progression‐free survival. These findings support testing for RAS/BRAF mutations in myeloma patients and underscore the potential therapeutic benefits of RAS/BRAF inhibitors.
Who, where, when: Colorectal cancer disparities by race and ethnicity, subsite, and stage
Authors: Primm Kristin M. , Malabay Andrea Joyce , Curry Taylor , Chang Shine 
Published: May 2023

AbstractBackgroundThere are well‐established disparities in colorectal cancer (CRC) outcomes between White and Black patients; however, assessments of CRC disparities for other racial/ethnic groups are limited.MethodsThe Surveillance, Epidemiology, and End Results database identified patients aged 50–74 years with CRC adenocarcinoma from 2000 to 2019. Trends in age‐adjusted incidence rates were computed by stage at diagnosis and subsite across five broad race/ethnic groups (White, Black, Asian/Pacific Islander [API], American Indian/Alaskan Native [AIAN], and Hispanic) and four API subgroups (East Asian, Southeast Asian, South Asian, and Pacific Islander) Multivariable logistic regression evaluated associations between race/ethnicity and diagnosis stage. Multivariable Cox proportional hazards models assessed differences in cause‐specific survival (CSS).ResultsHispanic, AIAN, Southeast Asian, Pacific Islander, and Black patients were 3% to 28% more likely than Whites to be diagnosed with distant stage CRC, whereas East Asian and South Asians had similar or lower risk of distant stage CRC. From Cox regression analysis, Black, AIAN, and Pacific Islanders also experienced worse CSS, while East Asian and South Asian patient groups experienced better CSS. No significant differences in CSS were observed among Hispanic, Southeast Asian, and White patients. When stratified by stage, Black patients had worse CSS across all stages (early, hazard ratio (HR) = 1.38; regional, HR = 1.22; distant, HR: 1.07, p < 0.05 for all).ConclusionDespite advances in CRC screening, treatment and early detection efforts, marked racial/ethnic disparities in incidence, stage at diagnosis, and survival persist. Findings demonstrate the extent to which aggregating heterogenous populations masks significant variability in CRC outcomes within race/ethnic subgroups.
MiR‐503 pleiotropically regulates epithelial‐mesenchymal transition and targets PTK7 to control lung cancer metastasis
Authors: Tsai Tzu‐Hsiu , Gow Chien‐Hung , Liu Yi‐Nan , Tsai Meng‐Feng , Chang Tzu‐Hua , Wu Shang‐Gin , Hsieh Min‐Shu , Su Kang‐Yi , Shih Jin‐Yuan 
Published: May 2023

AbstractObjectiveIn lung cancer patients, most deaths are caused by the distant dissemination of cancer cells. Epithelial–mesenchymal transition (EMT) and collective cell migration are distinct and important mechanisms involved in cancer invasion and metastasis. Additionally, microRNA dysregulation contributes significantly to cancer progression. In this study, we aimed to explore the function of miR‐503 in cancer metastasis.MethodsMolecular manipulations (silencing or overexpression) were performed to investigate the biological functions of miR‐503 including migration and invasion. Reorganization of cytoskeleton was assessed using immunofluorescence and the relationship between miR‐503 and downstream protein tyrosine kinase 7 (PTK7) was assessed using quantitative real‐time PCR, immunoblotting, and reporter assays. The tail vein metastatic animal experiments were performed.ResultsHerein, we demonstrated that the downregulation of miR‐503 confers an invasive phenotype in lung cancer cells and provided in vivo evidence that miR‐503 significantly inhibits metastasis. We found that miR‐503 inversely regulates EMT, identified PTK7 as a novel miR‐503 target, and showed the functional effects of miR‐503 on cell migration and invasion were restored upon reconstitution of PTK7 expression. As PTK7 is a Wnt/planar cell polarity protein crucial for collective cell movement, these results implicated miR‐503 in both EMT and collective migration. However, the expression of PTK7 did not influence EMT induction, suggesting that miR‐503 regulates EMT through mechanisms other than PTK7 inhibition. Furthermore, we discovered that PTK7 mechanistically activates focal adhesion kinase (FAK) and paxillin, thereby controlling the reorganization of the cortical actin cytoskeleton.ConclusionCollectively, miR‐503 is capable of governing EMT and PTK7/FAK signaling independently to control the invasion and dissemination of lung cancer cells, indicating that miR‐503 represents a pleiotropic regulator of cancer metastasis and hence a potential therapeutic target for lung cancer.
Clinical outcomes after CPX‐351 in patients with high‐risk acute myeloid leukemia: A comparison with a matched cohort from the Spanish PETHEMA registry
Authors: Bernal Teresa , Moreno Ainhoa Fernández , de LaIglesia Almudena , Benavente Celina , García‐Noblejas Ana , Belmonte Daniel García , Riaza Rosalía , Salamero Olga , Foncillas Maria Angeles , Roldán Alicia , Concepción Víctor Noriega , González Laura Llorente , Bergua Burgués Juan Miguel , Lorente de Uña Soraya , Rodríguez‐Macías Gabriela , de la Fuente Burguera Adolfo , García Pérez Maria José , López‐Lorenzo Jose Luis , Martínez Pilar , Aláez Concepción , Callejas Marta , Martínez‐Chamorro Carmen , Roca José Rifón , Barciela Lourdes Amador , Mena Durán Armando V. , Gómez Correcha Karoll , Lavilla Rubira Esperanza , Amigo María Luz , Vall‐llovera Ferran , Garrido Ana , García‐Fortes María , de Miguel Llorente Dunia , Leonardo Anastasia Aules , Cervero Carlos , Jordá Rosa Coll , Pérez‐Encinas Manuel M. , Zarzuela Marta Polo , Figuera Angela , Rad Guillermo , Martínez‐Cuadrón David , Montesinos Pau 
Published: May 2023

AbstractBackgroundCPX‐351 is approved for the treatment of therapy related acute myeloid leukemia (t‐AML) and AML with myelodysplastic related changes (MRC‐AML). The benefits of this treatment over standard chemotherapy has not been addressed in well matched cohorts of real‐life patients.MethodsRetrospective analysis of AML patients treated with CPX‐351 as per routine practice. A propensity score matching (PSM) was used to compare their main outcomes with those observed in a matched cohort among 765 historical patients receiving intensive chemotherapy (IC), all of them reported to the PETHEMA epidemiologic registry.ResultsMedian age of 79 patients treated with CPX‐351 was 67 years old (interquartile range 62–71), 53 were MRC‐AML. The complete remission (CR) rate or CR without recovery (CRi) after 1 or 2 cycles of CPX‐351 was 52%, 60‐days mortality 18%, measurable residual disease <0.1% in 54% (12 out of 22) of them. Stem cell transplant (SCT) was performed in 27 patients (34%), median OS was 10.3 months, and 3‐year relapse incidence was 50%. Using PSM, we obtained two comparable cohorts treated with CPX‐351 (n = 52) or IC (n = 99), without significant differences in CR/CRi (60% vs. 54%) and median OS (10.3 months vs. 9.1 months), although more patients were bridged to SCT in the CPX‐351 group (35% vs. 12%). The results were confirmed when only 3 + 7 patients were included in the historical cohort. In multivariable analyses, SCT was associated with better OS (HR 0.33 95% CI: 0.18–0.59), p < 0.001.ConclusionLarger post‐authorization studies may provide evidence of the clinical benefits of CPX‐351 for AML in the real‐life setting.
Orbitals‐Driven Insights on the Reactivity of Boron Oxide with Dioxygen for Methane Oxidation on Singlet and Triplet Spin States
Authors: Rawal Parveen , Gupta Puneet 
Published: May 2023

AbstractBoron‐based compounds such as frustrated Lewis pairs and borylenes that mimic transition‐metal(TM)‐like reactivity have attracted significant interest in recent years. This work examines the reactivity of boron oxide (B2O3) towards dioxygen for methane activation. Density functional theory in combination with orbital analysis were utilized to derive mechanistic pathways for methane‐to‐formaldehyde conversion over B2O3 in presence of closed‐shell singlet and triplet O2. Multiple pathways were screened on the triplet spin state. Best route via the triplet spin state depicts the interaction of B2O3 with dioxygen (O1=O2) and CH4 at a barrier of 49.8 kcal mol−1, to produce an intermediate having a B−O1−O2H unit and a free CH3 radical, which later react together at a barrier of 57.6 kcal mol−1, to finally yield HCHO. In the singlet spin state, a free CH3 radical does not form instead an intermediate with a B−O1−O2−CH3 unit is found after crossing a barrier of 41.1 kcal mol−1, which further undergoes via a relatively lower barrier of 23.4 kcal mol−1 to yield HCHO. Thus, the singlet pathway is energetically preferred over the triplet one. Orbitals further capture that at singlet and triplet states, methane activation follows a hydride and a hydrogen‐atom‐transfer mechanism, respectively.
Considerations for the Scale‐up of in vitro Transaminase‐Catalyzed Asymmetric Synthesis of Chiral Amines
Authors: Madsen Julie Østerby , Woodley John M. 
Published: May 2023

AbstractIn vitro transaminase catalyzed asymmetric synthesis is not a new phenomenon in the biocatalytic toolbox. Our group published a review on process consideration for these reactions in 2011, in which process metrics and the unfavorable reaction equilibrium was deduced to be the main bottlenecks at the time. Now, a decade later, this has been solved by different process methods presented in this review, with the development of enzymatic cascades one of the main solutions. Today, the new bottleneck is the downstream processing, due to the complexity of transaminase reactions, in which a ketone and an amine as substrates and a new ketone and a new amine as products. How to recover the produced amine from the resulting product mixture is considered and will be the key challenge for scale‐up of such systems in the near future.
Effect of Polymeric Ligand Grafting Region on Confined Assembly of Gold Nanorods in cylindrical nanopores
Authors: Li Fan , Gong Xianxian , Ren Rui , Xiong Bijin , Zhu Jintao 
Published: May 2023

AbstractThe grafting region of polymeric ligands exhibit a significant influence on the assembly behavior of polymer tethered gold nanorods (AuNRs) in confined space. In this work, the effect of core size, molecular weight and grafting region of ligands on the assembly structure in cylindrical nanopores was investigated. It is found that polystyrene end‐tethered AuNR (AuNR@End−PS) exhibits a dumbbell‐like shape, while the AuNR with PS tethered on the entire surface (AuNR@Full−PS) shows a rod‐like morphology that gradually transforms into a spherical shape as the molecular weight increases. AuNR@End−PS is affected by the special steric hindrance at both ends, and prefers to form special structures such as inclination arrangement, whereas AuNR@Full−PS prefers to be arranged shoulder‐to‐shoulder in a chain‐like assembly. The confinement effect was studied as well by varying the diameter of pores. The results show that the nanoparticles prefer to arrange into a regular and ordered assembly structure in the strong confinement spaces. Under the synergy of confined spaces and ligands at both ends, the AuNRs@End−PS are more likely to form a tilted order‐assembly structure. The results of this work could provide new ideas and guidance for the preparation of ordered assembly of AuNRs with novel structures.
The Best of Both Worlds: Combining the Power of MICs and WCAs To Generate Stable and Crystalline CrI‐Tetracarbonyl Complexes with π‐Accepting Ligands
Authors: Bens Tobias , Walter Robert R. M. , Beerhues Julia , Schmitt Manuel , Krossing Ingo , Sarkar Biprajit 
Published: May 2023

AbstractHere we present stable and crystalline chromium(I) tetracarbonyl complexes with pyridyl‐MIC (MIC=mesoionic carbene) ligands and weakly coordinating anions (WCA=[Al(ORF)4]−, RF=C(CF3)3 and BArF=[B(ArF)4]−, ArF=3,5‐(CF3)2C6H3). The complexes were fully characterized via crystallographic, spectroscopic and theoretical methods. The influence of counter anions on the IR and EPR spectroscopic properties of the CrI complexes was investigated, and the electronic innocence versus non‐innocence of WCAs was probed. These are the first examples of stable and crystalline [Cr(CO)4]+ complexes with a chelating
accepting ligand, and the data presented here are of relevance for both the photochemical and the electrochemical properties of these classes of compounds.
Sulfur Dioxide Oxidation by Zinc and Zinc Oxide Nitrate/Nitrite Complexes in the Gas Phase: An Interplay between Redox‐Active Ligands and Metal
Authors: Salvitti Chiara , Bandeira Nuno A. G. , Pepi Federico , de Petris Giulia , Troiani Anna 
Published: May 2023

AbstractDifferent oxidative pathways of sulfur dioxide promoted by ZnO(NO3)2−, Zn(NO3)2−and Zn(NO2)(NO3)−are revealed by a joint investigation by mass spectrometry and theoretical calculations. The reactions are triggered by [Zn2+‐O−⋅]+or by the low‐valence Zn+through oxygen ion transfer or electron transfer to SO2, respectively. The NOx−ligands intervene in the oxidation only when sulfur dioxide is converted to SO3−or SO2−, leading to the formation of zinc sulfate and zinc sulfite coordinated to nitrate or nitrite anions. Kinetic analyses show that the reactions are fast and efficient, and theory discloses the elementary steps, namely oxygen ion transfer, oxygen atom transfer and electron transfer, occurring through similar energy landscapes for the three reactive anions.