bluuebunny/crossref_metadata_2025_split huggingface dataset:
Self‐Supported Catalytic Electrode of CoW/Co‐Foam Achieves Efficient Ammonia Synthesis at Ampere‐Level Current Density
Authors: Kang Xia , Yang Xue‐Jing , Meng Zhe , Sun Xue‐Feng , Shi Miao‐Miao , Li Hong‐Rui , Gao Rui , Bi Bo , Liu Dong‐Xue , Yan Jun‐Min , Jiang Qing 
Published: December 2023

AbstractConversion of air and water into valuable chemicals of ammonia (NH3) by plasma activation and electrochemical reduction is a promising approach to achieve zero carbon‐emission synthesis of NH3. However, designing highly efficient electrochemical catalysts is one of the key challenges in accomplishing this strategy. Herein, a self‐supported cobalt–tungsten alloy supported on cobalt foam (CoW/CF) is developed via a simple and efficient method at room temperature. Surprisingly, the catalyst exhibits ultra‐high NH3 partial current density (1559 mA cm−2), superior NH3 yield rate (164.3 mg h−1 cm−2), and high Faradaic efficiency (98.1%) under the condition of 0.2 M nitrate/nitrite, outperforming most of the reported values of electrosynthesis of NH3 to the knowledge. The introduction of W makes the Co atom surface electron deficient, which can enhance the adsorption of NOx− and mitigate the excessive bonding of hydroxyl radicals (OH*) generated during nitrite (NO2*) hydrogenation, thereby reducing the energy barrier of the potential‐determining step. More interestingly, a scale‐up reaction system is established, achieving an NH3 yield rate of 4.771 g h−1 and successfully converting the NH3 in solution into solid NH4Cl. The aforementioned progress significantly enhances the facilitation of NH3 electrosynthesis industrialization.
De novo assembly of frustrated Lewis pair bearing metal‐organic frameworks for atmospheric CO2 cycloaddition
Authors: Lu Youluan , Wu Haonan , Li Dongna , Huang Yi , Guo Huijuan , Wang Tielin , Shi Lijuan , Yi Qun 
Published: December 2023

AbstractPorous frustrated Lewis pairs (FLPs) have been demonstrated as cutting‐edge heterogeneous catalysts in acidic–basic catalysis, which, yet faces great challenges in synthesis. Herein, we propose a one‐step de novo assembly strategy for constructing porous FLPs by capping monodentate ionic liquids (ILs) on metal clusters during the synthesis of metal–organic frameworks (MOFs). The capping of ILs makes adjacent metal sites on MOFs transforming to coordinatively‐unsaturated metal Lewis acids, producing FLPs containing Lewis basic Cl− ions from ILs and metal sites. The distribution of ILs on the framework of MOFs endows the catalysts with large surface areas (up to 2125 m2 g−1), open channels and good stability. The porous FLPs behave unprecedented activity for atmospheric CO2 activation and coupling with epoxides (25–40°C, 1 bar, without cocatalyst). This de novo assembly strategy exhibits good universality for synthesizing porous FLPs from different kinds of ILs, paving a facile approach for designing high‐efficiency acidic–basic catalysts.
Double somatic mosaicism in Cornelia de Lange syndrome
Authors: Pezzani Lidia , Pezzoli Laura , Rosina Erica , Scatigno Agnese , Cereda Anna , Lucca Camilla , Bellini Matteo , Marchetti Daniela , Maino Marzia , Mangili Giovanna , Selicorni Angelo , Iascone Maria 
Published: December 2023

AbstractPost‐zygotic mosaicism is a well‐known biological phenomenon characterized by the presence of genetically distinct lineages of cells in the same individual due to post‐zygotic de novo mutational events. It has been identified in about 13% of Cornelia de Lange (CdLS) syndrome patients with a molecular diagnosis, an unusual high frequency. Here, we report the case of a patient affected by classic CdLS harboring post‐zygotic mosaicism for two different likely pathogenic variants at the same nucleotide position in NIPBL. Double somatic mosaicism has never been reported in CdLS and only rarely recognized in human diseases. Possible pathogenetic mechanisms are discussed.
Design of Organic Radical Cations as Potent Hydrogen‐Atom Transfer Catalysts for C−H Functionalization
Authors: Matsumoto Akira , Maruoka Keiji 
Published: December 2023

AbstractHydrogen‐atom transfer (HAT) catalysis offers an atom‐ and step‐economical approach to the direct functionalization of aliphatic C−H bonds. While the structure of HAT catalysts largely affects the reactivity and selectivity in the step where the C−H bond is cleaved, the choice of viable catalysts for HAT from strong C−H bonds is limited. The recent development of organic HAT catalysts based on the flexibly modifiable molecular platform has enabled fine‐tuning of the steric and electronic properties of these catalysts, thus greatly expanding their structural diversity. This review focuses on the design of HAT catalysts with cationic moieties as common structural motifs and their application to the selective manipulation of the C−H bonds of challenging substrates, including unactivated hydrocarbons.
Orbital Engineering Mediated by Cation Conjugation in Luminescent Uranyl‐Organic Hybrid Materials
Authors: Raghavan Adharsh , Cahill Christopher L. 
Published: December 2023

AbstractA series of compounds of the form [HAr]2[UO2X4] is reported here, wherein Ar is systematically varied between pyridine (1‐X), quinoline (2‐X), acridine (3‐X), 2,5‐dimethylpyrazine (4‐X), quinoxaline (5‐X), and phenazine (6‐X), and X=Cl or Br. With greater conjugation in the organic cation, a larger quenching in uranyl luminescence is observed in the solid state. Supporting our luminescence experiments with computation, we map out the potential energy diagrams for the singlet and triplet states of both the [HAr]+ cations and [UO2Cl4]2− anion in the crystalline state, and of the assembly. The distinct energy transfer pathways in each compound are discussed.
Identification of Crucial Photosensitizing Factors to Promote CO2‐to‐CO Conversion
Authors: Wang Ping , Guo Song , Zhao Qiu‐Ping , Xu Shen‐Yue , Lv Hongjin , Lu Tong‐Bu , Zhang Zhi‐Ming 
Published: December 2023

AbstractThe sensitizing ability of a catalytic system is closely related to the visible‐light absorption ability, excited‐state lifetime, redox potential, and electron‐transfer rate of photosensitizers (PSs), however it remains a great challenge to concurrently mediate these factors to boost CO2 photoreduction. Herein, a series of Ir(III)‐based PSs (Ir‐1–Ir‐6) were prepared as molecular platforms to understand the interplay of these factors and identify the primary factors for efficient CO2 photoreduction. Among them, less efficient visible‐light absorption capacity results in lower CO yields of Ir‐1, Ir‐2 or Ir‐4. Ir‐3 shows the most efficient photocatalytic activity among these mononuclear PSs due to some comprehensive parameters. Although the Kobs of Ir‐3 is ≈10 times higher than that of Ir‐5, the CO yield of Ir‐3 is slightly higher than that of Ir‐5 due to the compensation of Ir‐5’s strong visible‐light‐absorbing ability. Ir‐6 exhibits excellent photocatalytic performance due to the strong visible‐light absorption ability, comparable thermodynamic driving force, and electron transfer rate among these PSs. Remarkably, the CO2 photoreduction to CO with Ir‐6 can achieve 91.5 μmol, over 54 times higher than Ir‐1, and the optimized TONC‐1 can reach up to 28160. Various photophysical properties of the PSs were concurrently adjusted by fine ligand modification to promote CO2 photoreduction.
Stabilization of NH− Group Adjacent to Naked Silicon(II) Atom in Base Stabilized Aminosilylenes
Authors: Pandey Madhusudan K. , Hendi Zohreh , Wang Xiaobai , Bhandari Anirban , Singh Mukesh K. , Rachuy Katharina , Kumar Kushvaha Saroj , Herbst‐Irmer Regine , Stalke Dietmar , Roesky Herbert W. 
Published: December 2023

AbstractAminosilylene, comprising reactive NH− and Si(II) sites next to each other, is an intriguing class of compounds due to its ability to show diverse reactivity. However, stabilizing the reactive NH− group next to the free Si(II) atom is challenging and has not yet been achieved. Herein, we report the first examples of base stabilized free aminosilylenes Ar*NHSi(PhC(NtBu)2) (1 a) and Mes*NHSi(PhC(NtBu)2) (1 b) (Ar*=2,6‐dibenzhydryl‐4‐methylphenyl and Mes*=2,4,6‐tri‐tert‐butylphenyl), tolerating a NH− group next to the naked Si(II) atom. Remarkably, 1 a and 1 b exhibited interesting differences in their reactivity upon heating. With 1 a, an intramolecular C(sp3)−H activation of one of the benzhydryl methine hydrogen atoms to the Si(II) atom produced the five‐membered cyclic silazane 2. However, with 1 b, a rare 1,2‐hydrogen shift to the Si(II) atom afforded a silanimine 3, with a hydride ligand attached to an unsaturated silicon atom. Further, the coordination capabilities of 1 a were also tested with Ru(II) and Fe(0) precursors. Treatments of 1 a with [Ru(η6‐p‐cymene)Cl2]2 led to the isolation of a η6‐arene tethered complex [RuCl2{Ar*NHSi(PhC(tBuN)2)‐κ1‐Si‐η6‐arene}] (4), whereas with the Fe(CO)5 precursor a Fe(0) complex [Fe(CO)4{Ar*NHSi(PhC(tBuN)2)‐κ1‐Si}] (5) was obtained. Density functional theory (DFT) calculations were conducted to shed light on the structural, bonding, and energetic aspects in 1–5.
Photolysis mechanism of Di(tert‐butylphenyl)iodonium salt using 2‐isopropylthioxanthone as a sensitizer
Authors: Masuda Mayu , Shiraishi Atsushi , Kobayashi Ayumi , Iritani Kohei , Yamashita Takashi 
Published: December 2023

AbstractDiaryliodonium salts (Ar2I+X−) are used as a photosensitive initiator that generates acid or radical species by ultraviolet light irradiation. Recently, sensitization of Ar2I+X− has gained importance owing to the escalating demand for high‐sensitive initiators with longer wavelength absorption such as 365 and 436 nm. However, the mechanism of photolysis of Ar2I+X− has not been strictly elucidated. This paper shows discussions of the details of its mechanism. Herein, we analyzed the photosensitization of Ar2I+X− with 2–isopropylthioxanthone (ITX) based on transient absorption techniques. As a result, it was revealed that electron transfer occurred from a triplet excited state of ITX to Ar2I+X− with an electron transfer rate constant of 4.2 × 109 s−1. Furthermore, high performance liquid chromatography measurements found the quantum yield of the photolysis was determined to be 0.48.
Extraction, separation and purification of fatty acid ethyl esters for biodiesel and DHA from Thraustochytrid biomass
Authors: Singh Dilip , Rani Rekha , Sharma Ajay K. , Gupta Ravi P. , Ramakumar Sankara Sri Venkata , Mathur Anshu S. 
Published: December 2023

AbstractA novel approach for in situ transesterification, extraction, separation, and purification of fatty acid ethyl esters (FAEE) for biodiesel and docosahexaenoic acid (DHA) from Thraustochytrid biomass has been developed. The downstream processing of Thraustochytrids oil necessitates optimization, considering the higher content of polyunsaturated fatty acids (PUFA). While two‐step methods are commonly employed for extracting and transesterifying oil from oleaginous microbes, this may result in oxidation/epoxidation of omega‐3 oil due to prolonged exposure to heat and oxygen. To address this issue, a rapid single‐step method was devised for in situ transesterification of Thraustochytrid oil. Through further process optimization, a 50% reduction in solvent requirement was achieved without significantly impacting fatty acid recovery or composition. Scale‐up studies in a 4 L reactor demonstrated complete FAEE recovery (99.98% of total oil) from biomass, concurrently enhancing DHA yield from 16% to nearly 22%. The decolorization of FAEE oil with fuller's earth effectively removed impurities such as pigments, secondary metabolites, and waxes, resulting in a clear, shiny appearance. High‐performance liquid chromatography (HPLC) analysis indicated that the eluted DHA was over 94.5% pure, as corroborated by GC‐FID analysis.
Effect of co‐substitution on complex thermoelectric compounds: The Zintl phase Ba1‐xSrxZn2‐yCuySb2 system
Authors: Jeong Jiwon , Shim Daewon , Choi Myung‐Ho , Ok Kang Min , You Tae‐Soo 
Published: December 2023

AbstractThree co‐substituted quaternary and quinary Zintl phases belonging to the Ba1‐xSrxZn2‐yCuySb2 (x = 0, 0.09; 0.24 ≤ y ≤ 0.42) system were prepared by the molten Pb metal‐flux method. Co‐substitution using the cationic Sr and anionic Cu for Ba and Zn was initially applied to lower the thermal conductivities and to improve the electric conductivities of these title compounds simultaneously. The homogeneities of single‐phase products were verified by powder x‐ray diffraction analysis, and the BaCu2S2‐type orthorhombic crystal structures with the Ba/Sr and the Zn/Cu mixed‐sites were refined by single crystal x‐ray diffraction analysis. Structural selectivity for the observed BaCu2S2‐type phase was rationalized by the radius ratio of cationic and anionic elements, where r+/r− > 1. DFT calculations using the three structural models revealed that the Sr and Cu substitutions can increase the structural stability and the hole carrier concentration. A series of temperature‐dependent electrical transport property measurements for BaZn1.76Cu0.24Sb2 and Ba0.91Sr0.09Zn1.70Cu0.30Sb2 successfully proved that the co‐substitution using Sr and Cu enhanced electrical conductivities, but reduced the Seebeck coefficients resulting in the slight change in power factor.
Photothermal Prussian blue nanoparticles generate potent multi‐targeted tumor‐specific T cells as an adoptive cell therapy
Authors: Sweeney Elizabeth E. , Sekhri Palak , Muniraj Nethaji , Chen Jie , Feng Sally , Terao Joshua , Chin Samantha J. , Schmidt Danielle E. , Bollard Catherine M. , Cruz Conrad Russell Y. , Fernandes Rohan 
Published: December 2023

AbstractPrussian blue nanoparticle‐based photothermal therapy (PBNP‐PTT) is an effective tumor treatment capable of eliciting an antitumor immune response. Motivated by the ability of PBNP‐PTT to potentiate endogenous immune responses, we recently demonstrated that PBNP‐PTT could be used ex vivo to generate tumor‐specific T cells against glioblastoma (GBM) cell lines as an adoptive T cell therapy (ATCT). In this study, we further developed this promising T cell development platform. First, we assessed the phenotype and function of T cells generated using PBNP‐PTT. We observed that PBNP‐PTT facilitated CD8+ T cell expansion from healthy donor PBMCs that secreted IFNγ and TNFα and upregulated CD107a in response to engagement with target U87 cells, suggesting specific antitumor T cell activation and degranulation. Further, CD8+ effector and effector memory T cell populations significantly expanded after co‐culture with U87 cells, consistent with tumor‐specific effector responses. In orthotopically implanted U87 GBM tumors in vivo, PBNP‐PTT‐derived T cells effectively reduced U87 tumor growth and generated long‐term survival in >80% of tumor‐bearing mice by Day 100, compared to 0% of mice treated with PBS, non‐specific T cells, or T cells expanded from lysed U87 cells, demonstrating an enhanced antitumor efficacy of this ATCT platform. Finally, we tested the generalizability of our approach by generating T cells targeting medulloblastoma (D556), breast cancer (MDA‐MB‐231), neuroblastoma (SH‐SY5Y), and acute monocytic leukemia (THP‐1) cell lines. The resulting T cells secreted IFNγ and exerted increased tumor‐specific cytolytic function relative to controls, demonstrating the versatility of PBNP‐PTT in generating tumor‐specific T cells for ATCT.
Rescue of p53 functions by in vitro‐transcribed mRNA impedes the growth of high‐grade serous ovarian cancer
Authors: Raab Monika , Kostova Izabela , Peña‐Llopis Samuel , Fietz Daniela , Kressin Monika , Aberoumandi Seyed Mohsen , Ullrich Evelyn , Becker Sven , Sanhaji Mourad , Strebhardt Klaus 
Published: December 2023

AbstractBackgroundThe cellular tumor protein p53 (TP53) is a tumor suppressor gene that is frequently mutated in human cancers. Among various cancer types, the very aggressive high‐grade serous ovarian carcinoma (HGSOC) exhibits the highest prevalence of TP53 mutations, present in >96% of cases. Despite intensive efforts to reactivate p53, no clinical drug has been approved to rescue p53 function. In this study, our primary objective was to administer in vitro‐transcribed (IVT) wild‐type (WT) p53‐mRNA to HGSOC cell lines, primary cells, and orthotopic mouse models, with the aim of exploring its impact on inhibiting tumor growth and dissemination, both in vitro and in vivo.MethodsTo restore the activity of p53, WT p53 was exogenously expressed in HGSOC cell lines using a mammalian vector system. Moreover, IVT WT p53 mRNA was delivered into different HGSOC model systems (primary cells and patient‐derived organoids) using liposomes and studied for proliferation, cell cycle progression, apoptosis, colony formation, and chromosomal instability. Transcriptomic alterations induced by p53 mRNA were analyzed using RNA sequencing in OVCAR‐8 and primary HGSOC cells, followed by ingenuity pathway analysis. In vivo effects on tumor growth and metastasis were studied using orthotopic xenografts and metastatic intraperitoneal mouse models.ResultsReactivation of the TP53 tumor suppressor gene was explored in different HGSOC model systems using newly designed IVT mRNA‐based methods. The introduction of WT p53 mRNA triggered dose‐dependent apoptosis, cell cycle arrest, and potent long‐lasting inhibition of HGSOC cell proliferation. Transcriptome analysis of OVCAR‐8 cells upon mRNA‐based p53 reactivation revealed significant alterations in gene expression related to p53 signaling, such as apoptosis, cell cycle regulation, and DNA damage. Restoring p53 function concurrently reduces chromosomal instability within the HGSOC cells, underscoring its crucial contribution in safeguarding genomic integrity by moderating the baseline occurrence of double‐strand breaks arising from replication stress. Furthermore, in various mouse models, treatment with p53 mRNA reduced tumor growth and inhibited tumor cell dissemination in the peritoneal cavity in a dose‐dependent manner.ConclusionsThe IVT mRNA‐based reactivation of p53 holds promise as a potential therapeutic strategy for HGSOC, providing valuable insights into the molecular mechanisms underlying p53 function and its relevance in ovarian cancer treatment.
The efficacy of immunotherapy and chemoimmunotherapy in patients with advanced rare tumors: A Turkish oncology group (TOG) study
Authors: Guven Deniz Can , Aykan Musa Baris , Muglu Harun , Bayram Ertugrul , Helvaci Kaan , Dursun Bengü , Celayir Melisa , Chelebiyev Elvin , Nayir Erdinc , Erman Mustafa , Sezer Ahmet , Urun Yuksel , Demirci Umut , Er Ozlem , Disel Umut , Bilici Ahmet , Arslan Cagatay , Karadurmus Nuri , Kilickap Saadettin 
Published: December 2023

AbstractIntroductionThe advances in immune checkpoint inhibitors (ICIs) were relatively slow in rare tumors. Therefore, we conducted a multi‐center study evaluating the efficacy of ICI monotherapy and the combination of ICIs with chemotherapy (CT) in patients with advanced rare tumors.MethodsIn this retrospective cohort study, we included 93 patients treated with ICIs for NCI‐defined rare tumors from the 12 cancer centers in Turkey. The primary endpoints were the overall response (ORR) and disease control rate (DCR).ResultsThe cohort's median age was 56, and 53.8% of the patients were male. The most frequent diagnosis was sarcoma (29%), and 81.7% of the patients were previously treated with at least one line of systemic therapy in the advanced stage.The ORR and DCR were 36.8% and 63.2%, respectively. The germ cell tumors had the lowest ORR (0%), while the Merkel cell carcinoma had the highest ORR to ICIs (57.1%). Patients treated with ICI + ICI or ICI plus chemotherapy combinations had higher ORR (55.2% vs. 27.6%, p = 0.012) and DCR (82.8% vs. 53.4%, p = 0.008).The median OS was 13.47 (95% CI: 7.79–19.15) months, and the six and 12‐month survival rates were 71% and 52%. The median duration of response was 16.59 months, and the 12‐month progression‐free survival rate was 66% in responders. The median time‐to‐treatment failure was 5.06 months (95% CI: 3.42–6.71). Three patients had high‐grade irAEs with ICIs (grade 3 colitis, grade 3 gastritis, and grade 3 encephalitis in one patient each).ConclusionWe observed over 30% ORR and a 13‐month median OS in patients with rare cancers treated with ICI monotherapy or ICI plus CT combinations. The response rates to ICIs or ICIs plus CT significantly varied across different tumor types. Responding patients had over 2 years of survival, highlighting a need for further trials with ICIs for patients with rare tumors.
Clinical implication of the Naples prognostic score on transcatheter aortic valve replacement in patients with severe aortic stenosis
Authors: Demirci Gökhan , Aslan Serkan , Güner Ahmet , Demir Ali R. , Erata Yunus E. , Türkmen İrem , Yalçın Ahmet A. , Kalkan Ali K. , Uzun Fatih , Çelik Ömer , Ertürk Mehmet 
Published: December 2023

AbstractBackgroundOne of the hallmarks of frailty in patients with severe aortic stenosis (AS) is malnutrition, for which one of the most up‐to‐date scoring systems is the Naples prognostic score (NPS). This study sought to investigate the predictive role of the NPS in determining mortality in patients undergoing transcatheter aortic valve replacement (TAVR) under long‐term follow‐up.MethodsA total of 430 consecutive patients with symptomatic severe AS who underwent TAVR were included retrospectively. The primary endpoint of the study was the long‐term all‐cause mortality. The study population was divided into two groups according to the NPS value, including Group 1 (NPS 0–2) and Group 2 (NPS 3–4).ResultsThe all‐cause mortality occurred in 250 patients (62.5%) patients during a follow‐up time of 40.6 (22.0–69.4) months. During the follow‐up period, all‐cause mortality was higher in Group 2 compared with Group 1 (87.9% vs. 42.9%, p < 0.001). Older age (p < 0.001), chronic obstructive pulmonary disease (p = 0.015), left ventricular ejection fraction (p = 0.021), and being in Group 2 (high NPS) (hazard ratio: 7.058, 95% confidence interval: 5.174–9.629, p < 0.001) were found to be independent predictors of all‐cause mortality at long‐term follow‐up.ConclusionThe NPS as a malnutrition and inflammation marker in patients with severe aortic stenosis who underwent TAVR provides valuable information for all‐cause mortality under long‐term follow‐up.
Percutaneous coronary intervention: Before, after, or during TAVR?
Authors: Hanson Ivan , Goldstein James A. 
Published: December 2023

Key points
Decisions surrounding if, and when, to perform coronary revascularization in patients undergoing trans‐catheter aortic valve replacement (TAVR) are often complex.
Concomitant percutaneous coronary interventions (PCI) and TAVR is associated with comparable technical success, but higher rates of bleeding and acute kidney injury, compared to staged procedures or no PCI.
Timing of PCI relative to TAVR should be individualized based on clinical status, lesion complexity and anticipated risks of bleeding and renal injury.