Dendrite growth of alkali metal anodes limited their lifetime for charge/discharge cycling. Here, we report near-perfect anodes of lithium, sodium, and potassium metals achieved by electrochemical ...polishing, which removes microscopic defects and creates ultra-smooth ultra-thin solid-electrolyte interphase layers at metal surfaces for providing a homogeneous environment. Precise characterizations by AFM force probing with corroborative in-depth XPS profile analysis reveal that the ultra-smooth ultra-thin solid-electrolyte interphase can be designed to have alternating inorganic-rich and organic-rich/mixed multi-layered structure, which offers mechanical property of coupled rigidity and elasticity. The polished metal anodes exhibit significantly enhanced cycling stability, specifically the lithium anodes can cycle for over 200 times at a real current density of 2 mA cm
with 100% depth of discharge. Our work illustrates that an ultra-smooth ultra-thin solid-electrolyte interphase may be robust enough to suppress dendrite growth and thus serve as an initial layer for further improved protection of alkali metal anodes.
The nonaqueous lithium–oxygen (Li–O2) battery is considered as one of the most promising candidates for next‐generation energy storage systems because of its very high theoretical energy density. ...However, its development is severely hindered by large overpotential and limited capacity, far less than theory, caused by sluggish oxygen redox kinetics, pore clogging by solid Li2O2 deposition, inferior Li2O2/cathode contact interface, and difficult oxygen transport. Herein, an open‐structured Co9S8 matrix with sisal morphology is reported for the first time as an oxygen cathode for Li–O2 batteries, in which the catalyzing for oxygen redox, good Li2O2/cathode contact interface, favorable oxygen evolution, and a promising Li2O2 storage matrix are successfully achieved simultaneously, leading to a significant improvement in the electrochemical performance of Li–O2 batteries. The intrinsic oxygen‐affinity revealed by density functional theory calculations and superior bifunctional catalytic properties of Co9S8 electrode are found to play an important role in the remarkable enhancement in specific capacity and round‐trip efficiency for Li–O2 batteries. As expected, the Co9S8 electrode can deliver a high discharge capacity of ≈6875 mA h g−1 at 50 mA g−1 and exhibit a low overpotential of 0.57 V under a cutoff capacity of 1000 mA h g−1, outperforming most of the current metal‐oxide‐based cathodes.
An open‐structured Co9S8 matrix with a sisal morphology is constructed and employed as oxygen cathode for Li–O2 batteries. Benefiting from its excellent interface between substrate and product, superior bifunctional catalytic activities, large accommodation for Li2O2, and easy diffusion for O2, the Co9S8 cathode exhibits excellent electrochemical performance, which is a very promising cathode for Li–O2 batteries.
Background
Circulating tumor DNA (ctDNA) has emerged as a noninvasive biomarker for dynamically monitoring tumors. However, published data on perioperative ctDNA in patients with operable non–small ...cell lung cancer (NSCLC) are currently limited.
Methods
This prospective study recruited 123 patients with resectable stage I to IIIA NSCLC. Preoperative and postoperative plasma samples and tumor tissue samples were subjected to next‐generation sequencing with a panel of 425 cancer‐related genes. Peripheral blood samples were collected before surgery, postoperatively within 1 month, and every 3 to 6 months for up to 3 years.
Results
After 4 exclusions, 119 eligible patients were enrolled from June 2016 to February 2019. Presurgical ctDNA was detectable in 29 of 117 patients (24.8%) and was associated with inferior recurrence‐free survival (RFS; hazard ratio HR, 2.42; 95% CI, 1.11‐5.27; P = .022) and inferior overall survival (OS; HR, 5.54; 95% CI, 1.01‐30.35; P = .026). Similarly, ctDNA was detected in 12 of 116 first postsurgical samples (10.3%) and was associated with shorter RFS (HR, 3.04; 95% CI, 1.22‐7.58; P = .012). During surveillance after surgery, longitudinal ctDNA–positive patients (37 of 119; 31.1%) had significantly shorter RFS (HR, 3.46; 95% CI, 1.59‐7.55; P < .001) and significantly shorter OS (HR, 9.99; 95% CI, 1.17‐85.78; P = .010) in comparison with longitudinal ctDNA–negative patients. Serial ctDNA detection preceded radiologic disease recurrence by a median lead time of 8.71 months.
Conclusions
These results suggest that perioperative ctDNA analyses can predict recurrence and survival, and serial ctDNA analyses can identify disease recurrence/metastasis earlier than routine radiologic imaging in patients with resectable NSCLC.
Lay Summary
The utility of serial circulating tumor DNA (ctDNA) monitoring for predicting disease recurrence and survival for early‐stage non–small cell lung cancer (NSCLC) has not been well characterized.
The detection of ctDNA before and after surgery is associated with the identification of a high risk of disease recurrence and long‐term patient outcomes for resectable NSCLC.
Perioperative ctDNA analyses identify disease recurrence earlier than routine radiologic imaging. ctDNA analyses can detect minimal residual disease for resectable NSCLC and thus can facilitate early intervention.
Perioperative circulating tumor DNA (ctDNA) analyses identify disease recurrence earlier than routine radiologic imaging. ctDNA analyses can detect minimal residual disease for resectable non–small cell lung cancer and thus can facilitate early intervention.
Cu is a unique catalyst for CO2 electroreduction, since it can catalyze CO2 reduction to a series of hydrocarbons, alcohols, and carboxylic acids. Nevertheless, such Cu catalysts suffer from poor ...selectivity. High pressure of CO2 is considered to facilitate the activity and selectivity of CO2 reduction. Herein, a new strategy is presented for CO2 reduction with improved C2H4 selectivity on a Cu catalyst by using CO2 capture materials as the support at ambient pressure. N‐doped carbon (NxC) was synthesized through high‐temperature carbonization of melamine and l‐lysine. We observed that the CO2 uptake capacity of NxC depends on both the microporous area and the content of pyridinic N species, which can be controlled by the carbonization temperature (600–800 °C). The as‐prepared CuO/NxC catalysts exhibit a considerably higher C2H4 faradaic efficiency (36 %) than CuO supported on XC‐72 carbon black (19 %), or unsupported CuO (20 %). Moreover, there is a good linear relationship between the C2H4 faradaic efficiency and CO2 uptake capacity of the supports for CuO. The local high CO2 concentration near Cu catalysts, created by CO2 capture materials, was proposed to increase the coverage of CO intermediate, which is favorable for the coupling of two CO units in the formation of C2H4. This study demonstrates that pairing Cu catalysts with CO2 capture supports is a promising approach for designing highly effective CO2 reduction electrocatalysts.
The higher the better: CuO supported on N‐doped carbon, a CO2 capture material, exhibits high faradaic efficiency for CO2 electroreduction. The higher CO2 uptake capacity, the higher C2H4 selectivity. The local high CO2 concentration near the Cu catalysts, created by the CO2 capture materials, is proposed to increase the coverage of CO intermediate, which is favorable for the coupling of two CO units in the formation of C2H4.
Monofluorinated alkyl compounds are of great importance in pharmaceuticals, agrochemicals and materials. Herein, we describe a direct nickel‐catalyzed monofluoromethylation of unactivated alkyl ...halides using a low‐cost industrial raw material, bromofluoromethane, by demonstrating a general and efficient reductive cross‐coupling of two alkyl halides. Results with 1‐bromo‐1‐fluoroalkane also demonstrate the viability of monofluoroalkylation, which further established the first example of reductive C(sp3)‐C(sp3) cross‐coupling fluoroalkylation. These transformations demonstrate high efficiency, mild conditions, and excellent functional‐group compatibility, especially for a range of pharmaceuticals and biologically active compounds. Mechanistic studies support a radical pathway. Kinetic studies reveal that the reaction is first‐order dependent on catalyst and alkyl bromide whereas the generation of monofluoroalkyl radical is not involved in the rate‐determining step. This strategy provides a general and efficient method for the synthesis of aliphatic fluorides.
A direct nickel‐catalyzed monofluoroalkylation of unactivated alkyl halides has been established, by demonstrating the first example of reductive C(sp3)−C(sp3) cross‐coupling fluoroalkylation. These transformations exhibited high efficiency, mild conditions, and excellent functional‐group compatibility, especially for a range of pharmaceuticals and biologically active compounds.
Despite the extremely high ionic conductivity, the commercialization of Li10GeP2S12-type materials is hindered by the poor stability against Li metal. Herein, to address that issue, a simple strategy ...is proposed and demonstrated for the first time, i.e., in situ modification of the interface between Li metal and Li10SnP2S12 (LSPS) by pretreatment with specific ionic liquid and salts. X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy results reveal that a stable solid electrolyte interphase (SEI) layer instead of a mixed conducting layer is formed on Li metal by adding 1.5 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/N-propyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr13TFSI) ionic liquid, where ionic liquid not only acts as a wetting agent but also improves the stability at the Li/LSPS interface. This stable SEI layer can prevent LSPS from directly contacting the Li metal and further decomposition, and the Li/LSPS/Li symmetric cell with 1.5 M LiTFSI/Pyr13TFSI attains a stable cycle life of over 1000 h with both the charge and discharge voltages reaching about 50 mV at 0.038 mA cm–2. Furthermore, the effects of different Li salts on the interfacial modification is also compared and investigated. It is shown that lithium bis(fluorosulfonyl) imide (LiFSI) salt causes the enrichment of LiF in the SEI layer and results in a higher resistance of the cell upon a long cycling life.
Summary
The objective of this study was to prepare and characterise the thermal complex particles (TCPs) based on heating food grade protein–polysaccharide electrostatic complexes. The soybean ...protein isolate (SPI), cationic polysaccharide (chitosan, CS) and anionic polysaccharide (carboxymethyl cellulose, CMC) were used. Turbidity, particle size, ζ‐potential and morphology of TCPs were measured. The results showed that SPI‐CS and SPI‐CMC soluble complexes were obtained at specific pHs and kept at high electrostatic repulsive force. The particle size and polydispersity index of stable SPI‐CS (pH 4.55/80 °C) and SPI‐CMC (pH 6.15/95 °C) TCPs were 286.6 nm/0.282 and 171.5 nm/0.298, respectively. We inferred that the re‐assembly of SPI after thermal denaturation resulted in the formation of TCPs. The pH and ionic strength sensitivity tests indicated that the TCPs with different properties can be controlled by pH, temperature and polysaccharide type during heating. These TCPs could be used to encapsulate food functional components which were thermal insensitive.
The formation, morphology and stability of the SPI/CS and SPI/CMC thermal complex particles.
Sorafenib is the first-line treatment of advanced hepatocellular carcinoma (HCC). However, there is a lack of validated biomarkers to predict sorafenib sensitivity. In this study we investigated the ...role of ACSL4, a positive-activating enzyme of ferroptosis, in sorafenib-induced cell death and HCC patient outcome. We showed that ACSL4 protein expression was negatively associated with IC
values of sorafenib in a panel of HCC cell lines (R = -0.952, P < 0.001). Knockdown of ACSL4 expression by specific siRNA/sgRNA significantly attenuated sorafenib-induced lipid peroxidation and ferroptosis in Huh7 cells, and also rescued sorafenib-induced inhibition of xenograft tumor growth in vivo. We selected 29 HCC patients with surgery as primary treatment and sorafenib as postoperative adjunct therapy from a hospital-based cohort. A high proportion (66.7%) of HCC patients who had complete or partial responses to sorafenib treatment (according to the revised RECIST guideline) had higher ACSL4 expression in the pretreated HCC tissues, compared with those who had stable or progressed tumor growth (23.5%, P = 0.029). Since ACSL4 expression was independent of sorafenib treatment, it could serve as a useful predictive biomarker. Taken together, this study demonstrates that ACSL4 is essential for sorafenib-induced ferroptosis and useful for predicting sorafenib sensitivity in HCC. This study may have important translational impacts in precise treatment of HCC.
Sorafenib is the first-line medication for advanced hepatocellular carcinoma (HCC), but it can only extend limited survival. It is imperative to find a combination strategy to increase sorafenib ...efficacy. Artesunate is such a preferred candidate, because artesunate is clinically well-tolerated and more importantly both drugs can induce ferroptosis through different mechanisms. In this study we investigated the combined effect of sorafenib and artesunate in inducing ferroptosis of HCC and elucidated the involved molecular mechanisms. We showed that artesunate greatly enhanced the anticancer effects of low dose of sorafenib against Huh7, SNU-449, and SNU-182 HCC cell lines in vitro and against Huh7 cell xenograft model in Balb/c nude mice. The combination index method confirmed that the combined effect of sorafenib and artesunate was synergistic. Compared with the treatment with artesunate or sorafenib alone, combined treatment induced significantly exacerbated lipid peroxidation and ferroptosis, which was blocked by N-acetyl cysteine and ferroptosis inhibitors liproxstatin-1 and deferoxamine mesylate, but not by inhibitors of other types of cell death (z-VAD, necrostatin-1 and belnacasan). In Huh7 cells, we demonstrated that the combined treatment induced oxidative stress and lysosome-mediated ferritinophagy, two essential aspects of ferroptosis. Sorafenib at low dose mainly caused oxidative stress through mitochondrial impairments and SLC7A11-invovled glutathione depletion. Artesunate-induced lysosome activation synergized with sorafenib-mediated pro-oxidative effects by promoting sequential reactions including lysosomal cathepsin B/L activation, ferritin degradation, lipid peroxidation, and consequent ferroptosis. Taken together, artesunate could be repurposed to sensitize sorafenib in HCC treatment. The combined treatment can be easily translated into clinical applications.
A nickel‐catalyzed direct trifluoroethylation of aryl iodides with an industrial raw material CF3CH2I has been developed, demonstrating high efficiency, excellent functional‐group compatibility, ...especially with large sterically hindered groups. The key to success is the combination of nickel with readily available nitrogen and phosphine ligands. The powerful potential of this strategy is further demonstrated by the late‐stage modification of several derived bioactive molecules.
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