25 research outputs found
Data from: Testing of Evaluation Bias for Progression Free Survival Endpoint in Oncology Clinical Trials
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
[C<sup>ā§</sup>NPtĀ(acac)] (C<sup>ā§</sup>N = cyclometalating
ligand; acac = acetylacetonato) complexes in which the naphthalimide
(NI) moiety is directly cyclometalated (NI as the C donor of the CāPt
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>ā§</sup>N ligand was prepared (<b>Pt-1</b>). Strong absorption of visible
light (ε = 21ā900 M<sup>ā1</sup> cm<sup>ā1</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> ā 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 tripletātriplet-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 CāH Carbonylation of Diarylamines Leading to Diversified Acridones under CO-Free Conditions
A Pd-catalyzed
dual CāH 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
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 (ā0.162 V), high current
density (6.1 mA/cm<sup>ā2</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>ā2</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 CāC Bond Formation via Dual CāH Bond Cleavage: αāPhenanthridinylation of Ether by Isocyanide
The
benzoyl peroxide-promoted α-phenanthridinylation of ether by
isocyanide is developed, proceeding through dual CāH bond cleavage
and dual CāC 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 CoāN<sub>4</sub> Sites Enable Near-Infrared Photooxidation
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
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 ālittle 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
Additional file 1: Figure S1. of Single- and double-walled carbon nanotubes enhance atherosclerogenesis by promoting monocyte adhesion to endothelial cells and endothelial progenitor cell dysfunction
Effects of SWCNTs and DWCNTs on cell viability. (PPTX 70 kb
Unveiling the Mechanism of Plasma-Catalyzed Oxidation of Methane to C<sub>2+</sub> Oxygenates over Cu/UiO-66-NH<sub>2</sub>
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 ā¼60.8% 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
CāC 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
CāC coupling and C2+ liquid formation. This work
provides valuable mechanistic insights into CāC 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