25 research outputs found

    Data from: Testing of Evaluation Bias for Progression Free Survival Endpoint in Oncology Clinical Trials

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    Progression free survival is an increasingly popular end point in oncology clinical trials. A complete blinded independent central review (BICR) is often required by regulators in an attempt to reduce the bias in PFS assessment. In this paper, we propose a new methodology that uses a sample-based BICR as an audit tool to decide whether a complete BICR is needed. More specifically, we propose a new index, the differential risk, to measure the reading discordance pattern, and develop a corresponding hypothesis testing procedure to decide whether the bias in local evaluation is acceptable. Simulation results demonstrate that our new index is sensitive to the change of discordance pattern; type I error is well controlled in the hypothesis testing procedure, and the calculated sample size provides the desired power

    Long-Lived Room Temperature Deep-Red/Near-IR Emissive Intraligand Triplet Excited State (<sup>3</sup>IL) of Naphthalimide in Cyclometalated Platinum(II) Complexes and Its Application in Upconversion

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    [C<sup>∧</sup>NPtĀ­(acac)] (C<sup>∧</sup>N = cyclometalating ligand; acac = acetylacetonato) complexes in which the naphthalimide (NI) moiety is directly cyclometalated (NI as the C donor of the C–Pt bond) were synthesized. With 4-pyrazolylnaphthalimide, isomers with five-membered (<b>Pt-2</b>) and six-membered (<b>Pt-3</b>) chelate rings were obtained. With 4-pyridinylnaphthalimide, only the complex with a five-membered chelate ring (<b>Pt-4</b>) was isolated. A model complex with 1-phenylpyrazole as the C<sup>∧</sup>N ligand was prepared (<b>Pt-1</b>). Strong absorption of visible light (ε = 21 900 M<sup>–1</sup> cm<sup>–1</sup> at 443 nm for <b>Pt-3</b>) and room temperature (RT) phosphorescence at 630 nm (<b>Pt-2</b> and <b>Pt-3</b>) or 674 nm (<b>Pt-4</b>) were observed. Long-lived phosphorescences were observed for <b>Pt-2</b> (Ļ„<sub>P</sub> = 12.8 μs) and <b>Pt-3</b> (Ļ„<sub>P</sub> = 61.9 μs). <b>Pt-1</b> is nonphosphorescent at RT in solution because of the acac-localized T<sub>1</sub> excited state [based on density functional theory (DFT) calculations and spin density analysis], but a structured emission band centered at 415 nm was observed at 77 K. Time-resolved transient absorption spectra and spin density analysis indicated a NI-localized intraligand triplet excited state (<sup>3</sup>IL) for complexes <b>Pt-2</b>, <b>Pt-3</b>, and <b>Pt-4</b>. DFT calculations on the transient absorption spectra (T<sub>1</sub> → T<sub><i>n</i></sub> transitions, <i>n</i> > 1) also support the <sup>3</sup>IL assignment of the T<sub>1</sub> excited states of <b>Pt-2</b>, <b>Pt-3</b>, and <b>Pt-4</b>. The complexes were used as triplet sensitizers for triplet–triplet-annihilation (TTA) based upconversion, and the results show that <b>Pt-3</b> is an efficient sensitizer with an upconversion quantum yield of up to 14.1%, despite its low phosphorescence quantum yield of 5.2%. Thus, we propose that the sensitizer molecules at the triplet excited state that are otherwise nonphosphorescent were involved in the TTA upconversion process, indicating that weakly phosphorescent or nonphosphorescent transition-metal complexes can be used as triplet sensitizers for TTA upconversion

    Palladium-Catalyzed Dual C–H Carbonylation of Diarylamines Leading to Diversified Acridones under CO-Free Conditions

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    A Pd-catalyzed dual C–H carbonylation of commercially available diarylamines using Co2(CO)8 as a safe CO source has been developed. This methodology provides a facile approach for the synthesis of diversified acridones in moderate to good yields. The protocol features good functional group compatibility, operational safety, easy scale-up, and versatile transformations

    Synergistic Effects between Doped Nitrogen and Phosphorus in Metal-Free Cathode for Zinc-Air Battery from Covalent Organic Frameworks Coated CNT

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    A covalent organic framework that is composed of hexachlorocyclotriphosphazene and dicyanamide has been coated on CNT to prepare metal-free oxygen reduction reaction catalyst through thermal polymerization of the Zn-air battery cathode. The N,P-codoped nanohybrids have highly porous structure and active synergistic effect between graphitic-N and -P, which promoted the electrocatalytic performance. The electrocatalysts exhibits remarkable half-wave potential (āˆ’0.162 V), high current density (6.1 mA/cm<sup>–2</sup>), good stability (83%), and excellent methanol tolerance for ORR in alkaline solution. Furthermore, the N,P-codoped nanohybrids were used as an air electrode for fabrication of a high performance Zn-air battery. The battery achieves a high open-circuit potential (1.53 V) and peak power density (0.255 W cm<sup>–2</sup>). Moreover, the effect of N,P codoping on the conjugate carbon system and the synergistic effect between graphitic-N and P have been calculated through density functional theory calculations, which are essentially in agreement with experimental data

    The Benzoyl Peroxide Promoted Dual C–C Bond Formation via Dual C–H Bond Cleavage: α‑Phenanthridinylation of Ether by Isocyanide

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    The benzoyl peroxide-promoted α-phenanthridinylation of ether by isocyanide is developed, proceeding through dual C–H bond cleavage and dual C–C bond formation. The procedure tolerates a series of functional groups, such as methyl, fluoro, chloro, acetyl, methoxy carbonyl, cyano, and trifluoromethyl. Thus, it represents a facile pathway leading to 6-substituted phenanthridine derivatives. The addition of radical to the isonitrile followed by a radical aromatic cyclization is involved in this transformation

    Carbon Materials Containing Single-Atom Co–N<sub>4</sub> Sites Enable Near-Infrared Photooxidation

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    Near-infrared light occupies 54.3% of the solar spectrum and has greater penetration depth, and its effective utilization is of great significance in the practical application of photocatalysis on a larger scale. However, the development of catalysts that can directly utilize near-infrared light is still a huge challenge. This paper proposes a strategy to directly utilize near-infrared light (excitation wavelength extending to 850 nm) by creating carbon material doped with a high-spin-state Co(II)-Nx single-atom site. In the near-infrared-light-irradiated photooxidation of 1,5-dihydroxynaphthalene, the yield of juglone can reach 45% without a significant decrease, even when the catalytic volume is increased by 20 times, which was much higher than that irradiated by 460 nm wavelength (reduced by about 23%). Our study sets the stage for fabricating stable NIR photocatalysts and provides a solution to directly enhance NIR photooxidation in a large-scale manner

    Remedying Defects in Carbon Nitride To Improve both Photooxidation and H<sub>2</sub> Generation Efficiencies

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    The outstanding visible light response of carbon nitride has aroused intense expectations regarding its photocatalysis, but it is impeded by the inevitable defects. Here, we report on a facile melamine-based defect-remedying strategy and resultant carbon nitride high-performance photocatalysts (R-C<sub>3</sub>N<sub>4</sub>). Melamine with amino groups and a triazine structure was selected as a ā€œlittle patchā€ to passivate and remedy various defects inside carbon nitride. Such a remedying effect has been comprehensively proven by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) analyses, and the ninhydrin test. In addition, their effects on photocatalysis were also individually confirmed by chemical methods, including cyano reduction reactions and deamination reactions. Furthermore, melamine remediation can result in g-C<sub>3</sub>N<sub>4</sub>/mpg-C<sub>3</sub>N<sub>4</sub> junctions, which also favors electron transfer and charge separation during the photocatalytic reaction. In order to explore its broader applications, R-C<sub>3</sub>N<sub>4</sub> was used as a photocatalyst for the photooxidation reaction of 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate (1,4-DHP) and simultaneous H<sub>2</sub> evolution. The conversion rates of 1,4-DHP and H<sub>2</sub> production catalyzed by R-C<sub>3</sub>N<sub>4</sub> were enhanced 2 and 6.5 times, respectively. This rational design is beneficial for the conversion of 1,4-DHP during the preparation of bioactive compounds and clean hydrogen production at the same time

    Unveiling the Mechanism of Plasma-Catalyzed Oxidation of Methane to C<sub>2+</sub> Oxygenates over Cu/UiO-66-NH<sub>2</sub>

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    Nonthermal plasma (NTP) offers the potential for converting CH4 with CO2 into liquid products under mild conditions, but controlling liquid selectivity and manipulating intermediate species remain significant challenges. Here, we demonstrate the effectiveness of the Cu/UiO-66-NH2 catalyst in promising the conversion of CH4 and CO2 into oxygenates within a dielectric barrier discharge NTP reactor under ambient conditions. The 10% Cu/UiO-66-NH2 catalyst achieved an impressive 53.4% overall liquid selectivity, with C2+ oxygenates accounting for ∼60.8% of the total liquid products. In situ plasma-coupled Fourier-transform infrared spectroscopy (FTIR) suggests that Cu facilitates the cleavage of surface adsorbed COOH species (*COOH), generating *CO and enabling its migration to the surface of Cu particles. This surface-bound *CO then undergoes C–C coupling and hydrogenation, leading to ethanol production. Further analysis using CO diffuse reflection FTIR and 1H nuclear magnetic resonance spectroscopy indicates that in situ generated surface *CO is more effective than gas-phase CO (g) in promoting C–C coupling and C2+ liquid formation. This work provides valuable mechanistic insights into C–C coupling and C2+ liquid production during plasma-catalytic CO2 oxidation of CH4 under ambient conditions. These findings hold broader implications for the rational design of more efficient catalysts for this reaction, paving the way for advancements in sustainable fuel and chemical production
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