The reaction mechanism of a high capacity lithium-and manganese-rich metal oxide, 0.4Li 2 MnO 3-0.6LiMn 0.5 Ni 0.5 O 2 , has been investigated at the atomic level. High-resolution synchrotron X-ray powder diffraction (HRPD) and X-ray absorption spectroscopy (XAS) were used, respectively, to evaluate the electrochemical charge and discharge reactions in terms of local and bulk structural changes, and variations in the oxidation states of the transition metal ions. Ni Kedge XAS data indicate the participation of nickel in reversible redox reactions, whereas Mn K-edge absorption spectra show that the manganese ions do not participate in the electrochemical reactions. Rietveld refinements of the oxygen occupancy during charge and discharge provide evidence of reversible oxygen release and re-accommodation by the host structure; this unique oxygen participation is likely the main reason for the anomalously high capacity of these electrodes. The HRPD data also show that during the early cycles, characteristic peaks of the Li 2 MnO 3 component disappear when charged to 4.7 V, but reappear on discharge to 2.5 V, consistent with a reversible lithium and oxygen extraction process. The results provide new insights into the charge compensation mechanisms that occur when high capacity, lithium-and manganese-rich electrode materials are electrochemically cycleda topic that is currently being hotly debated in the literature.
In
this study, Fourier transform ion cyclotron resonance mass spectrometry
(FT-ICR MS), combined with quadrupolar detection (QPD), was applied
for online liquid chromatography (LC) MS analysis of natural organic
matter (NOM). Although FT-ICR MS has emerged as an important analytical
technique to study NOM, there are few previous reports on online LC
FT-ICR MS analysis of NOM due to the long acquisition time (2–8
s) required to obtain high-resolution mass spectra. The QPD technique
provides a critical advantage over the conventional dipolar detection
(DPD) technique for LC-MS analysis because a spectrum with the same
resolving power can be obtained in approximately half the acquisition
time. QPD FT-ICR MS provides resolving powers (
) of ∼300000 and 170000 at m/z 400 with acquisition times per scan
of 1.2 and 0.8 s, respectively. The reduced acquisition time per scan
allows increased number of acquisitions in a given LC analysis time,
resulting in improved signal to noise (S/N) ratio and dynamic range in comparison to conventional
methods. For example, 40% and 100% increases in the number of detected
peaks were obtained with LC QPD FT-ICR MS, in comparison to conventional
LC DPD FT-ICR MS and direct-injection FT-ICR MS. It is also possible
to perform more quantitative comparison and molecular level investigation
of NOMs with 2 μg of a NOM sample. The data presented herein
demonstrate a proof of principle that QPD combined with LC FT-ICR
MS is a sensitive analytical technique that can provide comprehensive
information about NOM.
Purpose: Although first-line crizotinib treatment leads to clinical benefit in ROS1 þ lung cancer, high prevalence of crizotinib-resistant ROS1-G2032R (ROS1 G2032R ) mutation and progression in the central nervous system (CNS) represents a therapeutic challenge. Here, we investigated the antitumor activity of repotrectinib, a novel next-generation ROS1/TRK/ALKtyrosine kinase inhibitor (TKI) in ROS1 þ patient-derived preclinical models.Experimental Design: Antitumor activity of repotrectinib was evaluated in ROS1 þ patient-derived preclinical models including treatment-naïve and ROS1 G2032R models and was further demonstrated in patients enrolled in an on-going phase I/II clinical trial (NCT03093116). Intracranial antitumor activity of repotrectinib was evaluated in a brain-metastasis mouse model.Results: Repotrectinib potently inhibited in vitro and in vivo tumor growth and ROS1 downstream signal in treatment-naïve YU1078 compared with clinically available crizotinib, ceritinib, and entrectinib. Despite comparable tumor regression between repotrectinib and lorlatinib in YU1078-derived xenograft model, repotrectinib markedly delayed the onset of tumor recurrence following drug withdrawal. Moreover, repotrectinib induced profound antitumor activity in the CNS with efficient blood-brain barrier penetrating properties. Notably, repotrectinib showed selective and potent in vitro and in vivo activity against ROS1 G2032R . These findings were supported by systemic and intracranial activity of repotrectinib observed in patients enrolled in the on-going clinical trial.Conclusions: Repotrectinib is a novel next-generation ROS1-TKI with improved potency and selectivity against treatment-naïve and ROS1 G2032R with efficient CNS penetration. Our findings suggest that repotrectinib can be effective both as firstline and after progression to prior ROS1-TKI.
We have achieved heteroepitaxial stacking of a van der Waals (vdW) monolayer metal, 1T'-WTe 2 , and a semiconductor, 2H-WSe 2 , in which a distinctively low contact barrier was established across a clean epitaxial vdW gap. Our epitaxial 1T'-WTe 2 films were identified as a semimetal by low temperature transport and showed the robust breakdown current density of 5.0 × 10 7 A/cm 2 . In comparison with a series of planar metal contacts, our epitaxial vdW contact was identified to possess intrinsic Schottky barrier heights below 100 meV for both electron and hole injections, contributing to superior ambipolar field-effect transistor (FET) characteristics, i.e., higher FET mobilities and higher on−off current ratios at smaller threshold gate voltages. We discuss our observations around the critical roles of the epitaxial vdW heterointerfaces, such as incommensurate stacking sequences and absence of extrinsic interfacial defects that are inaccessible by other contact methods.
Tracking thermally induced reactions has always been challenging for electrode materials of electrochemical battery systems. Traditionally, a variety of calorimetric techniques and in situ XRD at elevated temperatures has been used to evaluate the thermal stability of electrode materials. These techniques are capable of providing variations in heat capacity, mass and average bulk composition of materials only. Herein, we report investigation of thermal characteristics of Li0.33Ni0.8Co0.15Al0.05O2 by using in situ soft XAS measurements in combination with XRD. Fluorescence yield and partial electron yield measurements are used simultaneously to obtain element selective surface and bulk information. Fluorescence yield measurements reveal no energy change of the absorption peak and thus no valence state change in the bulk. However, electron yield measurements indicate that NiO-type rock salt structure is formed at the surface at temperatures above 200°C while no evidence for a surface reaction near Co sites in investigated temperature range is found. These results clearly show that in situ soft XAS can give a unique understanding of the role of each element in the structural transformation under thermal abuse offering a useful guidance in developing new battery system with improved safety performance.
Sensitivity is an important factor determining successful mass spectrometry (MS) analysis of metabolome, protein, drugs, and environmental samples. Currently, nanoelectrospray ionization (ESI) is widely used as a sensitive ionization method. However, application of nano-ESI is limited to polar molecules and there is no atmospheric pressure ionization technique developed that can be used for MS analysis of low- and nonpolar compounds with sensitivity that can match with nano-ESI. Herein, we propose paper spray chemical ionization (PSCI) as an ionization technique that can be used to analyze low- and nonpolar aromatic compounds with high sensitivity. PSCI is based on paper spray ionization utilizing corona discharge phenomenon. PSCI can sensitively and quantitatively detect down to picogram (or femtomole) levels of low- and nonpolar aromatic compounds.
Owing to the increasing environmental and climate changes globally, there is an increasing interest in the molecular-level understanding of environmental organic compound mixtures, that is, the pursuit of complete and detailed knowledge of the chemical compositions and related chemical reactions.Environmental organic molecule mixtures, including those in air, soil, rivers, and oceans, have extremely complex and heterogeneous chemical compositions. For their analyses, ultrahigh-resolution and sub-ppb level mass accuracy, achievable using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), are important. FT-ICR MS has been successfully used to analyze complex environmental organic molecule mixtures such as natural, soil, particulate, and dissolved organic matter. Despite its success, many limitations still need to be overcome. Sample preparation, ionization, structural identification, chromatographic separation, and data interpretation are some key areas that have been the focus of numerous studies. This review describes key developments in analytical techniques in these areas to aid researchers seeking to start or continue investigations for the molecular-level understanding of environmental organic compound mixtures.
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