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1.
Small ; : e2404614, 2024 Jul 05.
Article in English | MEDLINE | ID: mdl-38966870

ABSTRACT

Modulating interfacial electrochemistry represents a prevalent approach for mitigating lithium dendrite growth and enhancing battery performance. Nevertheless, while most additives exhibit inhibitory characteristics, the accelerating effects on interfacial electrochemistry have garnered limited attention. In this work, perfluoromorpholine (PFM) with facilitated kinetics is utilized to preferentially adsorb on the lithium metal interface. The PFM molecules disrupt the solvation structure of Li+ and enhance the migration of Li+. Combined with the benzotrifluoride, a synergistic acceleration-inhibition system is formed. The ab initio molecular dynamics (AIMD) and density functional theory (DFT) calculation of the loose outer solvation clusters and the key adsorption-deposition step supports the fast diffusion and stable interface electrochemistry with an accelerated filling mode with C─F and C─H groups. The approach induces the uniform lithium deposition. Excellent cycling performance is achieved in Li||Li symmetric cells, and even after 200 cycles in Li||NCM811 full cells, 80% of the capacity is retained. This work elucidates the accelerated electrochemical processes at the interface and expands the design strategies of acceleration fluorinated additives for lithium metal batteries.

2.
BMC Surg ; 24(1): 174, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38824553

ABSTRACT

BACKGROUND: The purpose of this study was to investigate effect of liver Transplants (LT) with retrograde reperfusion on early postoperative recovery of liver function and its risk factors. METHODS: We conducted a retrospective analysis of clinical data from 136 liver transplantation (LT) patients at the 900th Hospital of the Chinese People's Liberation Army Joint Support Army, covering the period from January 2015 to January 2021. All participants provided informed consent, adhering to medical ethics guidelines. Patients were stratified into two groups based on the liver perfusion technique used: retrograde reperfusion (RTR, n = 108) and initial portal reperfusion (IPR, n = 28). Our study focused on a subset of 23 patients from each group to compare postoperative liver function recovery. The final analysis included 86 RTR and 28 IPR cases after excluding 8 RTR patients who underwent initial hepatic artery reperfusion and 14 who received simultaneous hepatic artery and portal vein reperfusion. Further subdivision within the RTR group identified 19 patients with early hepatic allograft dysfunction (EAD) and 67 without, allowing for an assessment of the influence of preoperative and intraoperative parameters, as well as perfusion methods, on EAD incidence post-LT. RESULTS: Alanine aminotransferase (ALT) was 329 (211 ~ 548) and 176 (98 ~ 282) U/L on the 3rd and 7th day after RTR, respectively, which was significantly lower than 451 (288 ~ 918) and 251 (147 ~ 430) U/L in the IPR group (Z =-1.979, -2.299, P = 0.048, 0.021). Aspartate aminotransferase (AST) on postoperative days 3, 5, and 7 was 252 (193, 522), 105 (79, 163), and 93 (41, 135) U/L in the RTR group, respectively; it was also significantly lower than 328 (251, 724), 179 (129, 306), and 150 (91, 200)U/L in the IPR group (Z=-2.212, -3.221, -2.979; P = 0.027, 0.001, 0.003). Logistic regression analysis showed that MELD score was an independent risk factor for EAD after LT. CONCLUSION: RTR LT is more favorable for patients' early postoperative liver function recovery. For patients undergoing LT for RTR, preoperative MELD score was an independent risk factor for their postoperative development of EAD.


Subject(s)
Liver Transplantation , Recovery of Function , Reperfusion , Humans , Male , Retrospective Studies , Female , Middle Aged , Risk Factors , Reperfusion/methods , Adult , Liver Function Tests , Liver/blood supply , Postoperative Complications/epidemiology , Postoperative Complications/prevention & control , Postoperative Complications/etiology
3.
JACS Au ; 4(6): 2211-2219, 2024 Jun 24.
Article in English | MEDLINE | ID: mdl-38938815

ABSTRACT

Molten NaF-BeF2 salt is widely considered a promising candidate to replace FLiBe in molten salt reactor applications, which is crucial to reducing the operating costs of the molten salt reactor. Studies on beryllium compounds are rarely conducted due to their volatility and high toxicity. Herein, the Be-F coordination structure of NaF/BeF2 mixed salts was investigated in-depth through various HT-NMR and solid-state NMR methods, which are optimized to be appropriate for the detection of beryllium compounds. It was found that Na2BeF4 and NaBeF3 crystals were transformed into amorphous tetrahedral coordinated networks when there was an increase in the BeF2 concentration in the mixed salts. The main coordinate structure comparisons between FNaBe and FLiBe were analyzed, which exhibit high similarity due to the covalent effect of Be-F bonding, demonstrating the theoretical feasibility of applying FNaBe salts as a substitute for FLiBe in MSR systems. In addition, the transition from the crystal phase to the amorphous phase occurred at a lower BeF2 concentration for FNaBe than that for FLiBe. This was further verified by the results of ab initio molecular dynamics (AIMD) simulation that FNaBe melts had more disordered structures, thus causing slight changes in their physical properties.

4.
Small ; : e2400390, 2024 May 22.
Article in English | MEDLINE | ID: mdl-38778736

ABSTRACT

Gel electrolytes are gaining attention for rechargeable Zn-ion batteries because of their high safety, high flexibility, and excellent comprehensive electrochemical performances. However, current gel electrolytes still perform at mediocre levels due to incomplete Zn salts dissociation and side reactions. Herein, an electrostatic-induced dual-salt strategy is proposed to upgrade gel electrolytes to tackle intrinsic issues of Zn metal anodes. The competitive coordination mechanism driven by electrostatic repulsion and steric hindrance of dual anions promotes zinc salt dissociation at low lithium salt addition levels, improving ion transport and mechanical properties of gel electrolytes. Li+ ions and gel components coordinate with H2O, reducing active H2O molecules and inhibiting associated side reactions. The dual-salt gel electrolyte enables excellent reversibility of Zn anodes at both room and low temperatures. Zn||Polyaniline cells using the dual-salt gel electrolyte exhibit a high discharge capacity of 180 mAh g-1 and long-term cycling stability over 180 cycles at -20 °C. The dual-salt strategy offers a cost-effective approach to improving gel electrolytes for high-performance flexible Zn-ion batteries.

5.
PeerJ Comput Sci ; 10: e1948, 2024.
Article in English | MEDLINE | ID: mdl-38660210

ABSTRACT

Fusarium head blight (FHB) is a destructive disease that affects wheat production. Detecting FHB accurately and rapidly is crucial for improving wheat yield. Traditional models are difficult to apply to mobile devices due to large parameters, high computation, and resource requirements. Therefore, this article proposes a lightweight detection method based on an improved YOLOv8s to facilitate the rapid deployment of the model on mobile terminals and improve the detection efficiency of wheat FHB. The proposed method introduced a C-FasterNet module, which replaced the C2f module in the backbone network. It helps reduce the number of parameters and the computational volume of the model. Additionally, the Conv in the backbone network is replaced with GhostConv, further reducing parameters and computation without significantly affecting detection accuracy. Thirdly, the introduction of the Focal CIoU loss function reduces the impact of sample imbalance on the detection results and accelerates the model convergence. Lastly, the large target detection head was removed from the model for lightweight. The experimental results show that the size of the improved model (YOLOv8s-CGF) is only 11.7 M, which accounts for 52.0% of the original model (YOLOv8s). The number of parameters is only 5.7 × 106 M, equivalent to 51.4% of the original model. The computational volume is only 21.1 GFLOPs, representing 74.3% of the original model. Moreover, the mean average precision (mAP@0.5) of the model is 99.492%, which is 0.003% higher than the original model, and the mAP@0.5:0.95 is 0.269% higher than the original model. Compared to other YOLO models, the improved lightweight model not only achieved the highest detection precision but also significantly reduced the number of parameters and model size. This provides a valuable reference for FHB detection in wheat ears and deployment on mobile terminals in field environments.

6.
J Mater Chem B ; 12(17): 4097-4117, 2024 May 01.
Article in English | MEDLINE | ID: mdl-38587869

ABSTRACT

Single phototherapy and immunotherapy have individually made great achievements in tumor treatment. However, monotherapy has difficulty in balancing accuracy and efficiency. Combining phototherapy with immunotherapy can realize the growth inhibition of distal metastatic tumors and enable the remote monitoring of tumor treatment. The development of nanomaterials with photo-responsiveness and anti-tumor immunity activation ability is crucial for achieving photo-immunotherapy. As immune adjuvants, photosensitizers and photothermal agents, manganese-based nanoparticles (Mn-based NPs) have become a research hotspot owing to their multiple ways of anti-tumor immunity regulation, photothermal conversion and multimodal imaging. However, systematic studies on the synergistic photo-immunotherapy applications of Mn-based NPs are still limited; especially, the green synthesis and mechanism of Mn-based NPs applied in immunotherapy are rarely comprehensively discussed. In this review, the synthesis strategies and function of Mn-based NPs in immunotherapy are first introduced. Next, the different mechanisms and leading applications of Mn-based NPs in immunotherapy are reviewed. In addition, the advantages of Mn-based NPs in synergistic photo-immunotherapy are highlighted. Finally, the challenges and research focus of Mn-based NPs in combination therapy are discussed, which might provide guidance for future personalized cancer therapy.


Subject(s)
Immunotherapy , Manganese , Humans , Manganese/chemistry , Manganese/pharmacology , Immunotherapy/methods , Phototherapy/methods , Green Chemistry Technology , Neoplasms/therapy , Neoplasms/drug therapy , Animals , Nanostructures/chemistry , Photosensitizing Agents/chemistry , Photosensitizing Agents/pharmacology , Photosensitizing Agents/chemical synthesis , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemical synthesis , Particle Size
7.
Angew Chem Int Ed Engl ; 63(14): e202317135, 2024 Apr 02.
Article in English | MEDLINE | ID: mdl-38332748

ABSTRACT

Organic electrode materials are promising for next-generation energy storage materials due to their environmental friendliness and sustainable renewability. However, problems such as their high solubility in electrolytes and low intrinsic conductivity have always plagued their further application. Polymerization to form conjugated organic polymers can not only inhibit the dissolution of organic electrodes in the electrolyte, but also enhance the intrinsic conductivity of organic molecules. Herein, we synthesized a new conjugated organic polymer (COPs) COP500-CuT2TP (poly [5,10,15,20-tetra(2,2'-bithiophen-5-yl) porphyrinato] copper (II)) by electrochemical polymerization method. Due to the self-exfoliation behavior, the porphyrin cathode exhibited a reversible discharge capacity of 420 mAh g-1, and a high specific energy of 900 Wh Kg-1 with a first coulombic efficiency of 96 % at 100 mA g-1. Excellent cycling stability up to 8000 cycles without capacity loss was achieved even at a high current density of 5 A g-1. This highly conjugated structure promotes COP500-CuT2TP combined high energy density, high power density, and good cycling stability, which would open new opportunity for the designable and versatile organic electrodes for electrochemical energy storage.

8.
J Cancer ; 14(8): 1381-1397, 2023.
Article in English | MEDLINE | ID: mdl-37283799

ABSTRACT

Background: Host cell factor 1 (HCFC1) was reported associated with the progression of a variety of cancers. However, its role in the prognosis and immunological characteristics of hepatocellular carcinoma (HCC) patients has not been revealed. Methods: The expression and prognostic value of HCFC1 in HCC were investigated from the Cancer Genome Atlas (TCGA) dataset and a cohort of 150 HCC patients. The associations between HCFC1 expression with somatic mutational signature, tumor mutational burden (TMB), and microsatellite instability (MSI) were investigated. Next, the correlation of HCFC1 expression with immune cell infiltration was investigated. In vitro, cytological experiments were conducted to verify the role of HCFC1 in HCC. Results: HCFC1 mRNA and protein upregulated in HCC tissues and correlated to poor prognosis. Multivariate regression analysis based on a cohort of 150 HCC patients revealed that high HCFC1 protein expression was an independent risk factor for prognosis. Upregulation of HCFC1 expression was associated with TMB, MSI, and tumor purity. HCFC1 expression showed a significant positive association with B cell memory, T cell CD4 memory, macrophage M0, and a significant positive association with immune checkpoint-related gene expression in the tumor microenvironment. HCFC1 expression negatively correlated to ImmuneScore, EstimateScore, and StromalScore. The single-cell RNA sequencing analysis demonstrated that the malignant cells and immune cells (B cells, T cells, and macrophages) represented high HCFC1 expression in HCC tissues. Functional analysis revealed that HCFC1 was remarkably correlated with cell cycle signaling. HCFC1 knockdown inhibited the proliferation, migration, and invasion capacity while promoting the apoptosis of HCC cells. At the same time, the cell-cycle-related proteins such as Cyclin D1 (CCND1), Cyclin A2 (CCNA2), cyclin-dependent kinase 4 (CDK4), and cyclin-dependent kinase 6 (CDK6) were downregulated. Conclusion: Upregulation of HCFC1 predicted undesirable prognosis of HCC patients and promoted tumor progression through inhibiting cell cycle arrest.

9.
Arch Biochem Biophys ; 743: 109661, 2023 07 15.
Article in English | MEDLINE | ID: mdl-37268273

ABSTRACT

BACKGROUND: Small nuclear ribonucleoprotein Sm D1 (SNRPD1) has been reported as an oncogene in some solid cancers. Our previous study suggested that SNRPD1 has diagnostic and prognostic value in hepatocellular carcinoma (HCC), but its role in tumor growth and biological behavior remains unknown. In this study, we aimed to unravel the role and mechanism of SNRPD1 in HCC. METHODS: We investigated the SNRPD1 mRNA level in adjacent normal liver tissues and HCC tissues with different tumor stages in the UALCAN database. The associations between SNRPD1 mRNA expression and HCC prognosis were investigated in TCGA database. Then, 52 pairs of frozen HCC tissues and corresponding adjacent normal liver tissues were collected to perform qPCR and immunohistochemistry assay. Next, we carried out a series of experiments in vitro and in vivo to investigate the effects of SNRPD1 expression on cell invasion, migration, proliferation, autophagy, and the PI3K/AKT/mTOR pathway. RESULTS: The bioinformatics analysis and qPCR in our patient cohort demonstrated that the SNRPD1 mRNA level in HCC tissues was higher than in adjacent normal tissues. In addition, the immunohistochemistry assay exhibited an increased SNRPD1 protein level with the tumor stage increase. Survival analysis suggested that higher expression of SNRPD1 was significantly associated with unfavorable prognosis of patients with HCC. The functional experiments in vitro indicated that SNRPD1 knockdown suppressed the cellular proliferation, migration, and invasion capacities. Furthermore, SNRPD1 inhibition induced cellular apoptosis and arrested the HCC cells at the G0/G1 phase of the cell cycle. Mechanistic analyses demonstrated that SNRPD1 knockdown induced the increase of autophagic vacuoles and the expression of autophagy-related genes (ATG5, ATG7, and ATG12) and blocked the PI3K/AKT/mTOR/4EBP1 pathway in vitro. Moreover, SNRPD1 inhibition suppressed tumor growth and expression of the Ki67 protein in vivo. CONCLUSIONS: SNRPD1 may serve as an oncogene in HCC and promote tumor proliferation via inhibiting autophagy induced through the PI3K/Akt/mTOR/4EBP1 pathway.


Subject(s)
Carcinoma, Hepatocellular , Liver Neoplasms , Humans , Autophagy , Carcinoma, Hepatocellular/pathology , Cell Line, Tumor , Cell Proliferation , Liver Neoplasms/pathology , Phosphatidylinositol 3-Kinases/metabolism , Proto-Oncogene Proteins c-akt/metabolism , RNA, Messenger , Signal Transduction , TOR Serine-Threonine Kinases/metabolism
10.
Front Oncol ; 13: 1134933, 2023.
Article in English | MEDLINE | ID: mdl-37124520

ABSTRACT

Background: This study aimed to investigate the role of the alpha fetoprotein (AFP) ratio before and after curative resection in the prognosis of patients with hepatocellular carcinoma (HCC) and to develop a novel pre- to postoperative AFP ratio nomogram to predict recurrence free survival (RFS) for HCC patients after curative resection. Methods: A total of 485 pathologically confirmed HCC patients who underwent radical hepatectomy from January 2010 to December 2018 were retrospectively analyzed. The independent prognostic factors of hepatocellular carcinoma were identified by multivariate COX proportional model analysis, and the nomogram model was constructed. The receiver operating characteristic and the C-index were used to evaluate the accuracy and efficacy of the model prediction, the correction curve was used to assess the calibration of the prediction model, and decision curve analysis was used to evaluate the clinical application value of the nomogram model. Results: A total of 485 HCC patients were divided into the training cohort (n = 340) and the validation cohort (n = 145) by random sampling at a ratio of 7:3. Using X-tile software, it was found that the optimal cut-off value of the AFP ratio in the training cohort was 0.8. In both cohorts, the relapse-free survival of patients with an AFP ratio <0.8 (high-risk group) was significantly shorter than in those with an AFP ratio ≥0.8 (low-risk group) (P < 0.05). An AFP ratio <0.8 was an independent risk factor for recurrence of HCC after curative resection. Based on the AFP ratio, BCLC stage and cirrhosis diagnosis, a satisfactory nomogram was developed. The AUC of our nomogram for predicting 1-, 3-, and 5-year RFS was 0.719, 0.690, and 0.708 in the training cohort and 0.721, 0.682, and 0.681 in the validation cohort, respectively. Furthermore, our model demonstrated excellent stratification as well as clinical applicability. Conclusion: The AFP ratio was a reliable biomarker for tumor recurrence. This easy-to-use AFP ratio-based nomogram precisely predicted tumor recurrence in HCC patients after curative resection.

11.
Aging (Albany NY) ; 15(7): 2610-2630, 2023 04 03.
Article in English | MEDLINE | ID: mdl-37014321

ABSTRACT

Hepatocellular carcinoma (HCC) remains imposing an enormous economic and healthcare burden worldwide. In this present study, we constructed and validated a novel autophagy-related gene signature to predict the recurrence of HCC patients. A total of 29 autophagy-related differentially expressed genes were identified. A five-gene signature (CLN3, HGF, TRIM22, SNRPD1, and SNRPE) was constructed for HCC recurrence prediction. Patients in high-risk groups exhibited a significantly poor prognosis compared with low-risk patients both in the training set (GSE14520 dataset) and the validation set (TCGA and GSE76427 dataset). Multivariate cox regression analysis demonstrated that the 5-gene signature was an independent risk factor for recurrence-free survival (RFS) in HCC patients. The nomograms incorporating 5-gene signature and clinical prognostic risk factors were able to effectively predict RFS. KEGG and GSEA analysis revealed that the high-risk group was enriched with multiple oncology characteristics and invasive-related pathways. Besides, the high-risk group had a higher level of immune cells and higher levels of immune checkpoint-related gene expression in the tumor microenvironment, suggesting that they might be more likely to benefit from immunotherapy. Finally, the immunohistochemistry and cell experiments confirmed the role of SNRPE, the most significant gene in the gene signature. SNRPE was significantly overexpressed in HCC. After SNRPE knockdown, the proliferation, migration and invasion ability of the HepG2 cell line were significantly inhibited. Our study established a novel five-gene signature and nomogram to predict RFS of HCC, which may help in clinical decision-making for individual treatment.


Subject(s)
Carcinoma, Hepatocellular , Liver Neoplasms , Humans , Hepatectomy , Carcinoma, Hepatocellular/genetics , Carcinoma, Hepatocellular/surgery , Liver Neoplasms/genetics , Liver Neoplasms/surgery , Autophagy/genetics , Computational Biology , Prognosis , Tumor Microenvironment/genetics , Membrane Glycoproteins , Molecular Chaperones
12.
Small ; 19(35): e2301569, 2023 Aug.
Article in English | MEDLINE | ID: mdl-37096921

ABSTRACT

In recent years, gel-electrolyte becomes pivotal in preventing hydrogen evolution, reducing dendrite growth, and protecting the zinc metal anode for zinc-ion batteries. Herein, a polyvinyl alcohol-based water-organic hybrid gel electrolyte with Agar and dimethyl sulfoxide is designed to construct the spontaneous desaturation of the solvation sheath for reducing hydrogen evolution and dendrite growth at room temperature and even low temperature. According to experimental characterization and theoretical calculations, the well binding between multihydroxy polymer and H2 O is achieved in the hybrid desaturated gel-electrolyte to regulate the inner and outer sheath. The ionic conductivity of hybrid gel-electrolyte reaches 7.4 mS cm-1 even at -20 °C with only 0.5 m zinc trifluoromethanesulfonate (Zn(OTf)2 ). The Zn symmetric cells cycle over 1200 h under 26 and -20 °C with improved mechanical properties and electrochemical performance. The asymmetric Zn || Cu cell with hybrid gel electrolyte reaches ≈99.02% efficiency after 250 cycles. The capacity of full cell is maintained at around 74 mAh g-1 with almost unchanged retention rate from 50 to 300 cycles at -20 °C. This work provides an effective strategy for desaturated solvation to reach anti-freezing and high-density Zn energy storage devices.

13.
Small ; 19(14): e2206563, 2023 Apr.
Article in English | MEDLINE | ID: mdl-36642823

ABSTRACT

Heterostructured materials integrate the advantages of adjustable electronic structure, fast electron/ions transfer kinetics, and robust architectures, which have attracted considerable interest in the fields of rechargeable batteries, photo/electrocatalysis, and supercapacitors. However, the construction of heterostructures still faces some severe problems, such as inferior random packing of components and serious agglomeration. Herein, a terminal group-oriented self-assembly strategy to controllably synthesize a homogeneous layer-by-layer SnSe2 and MXene heterostructure (LBL-SnSe2 @MXene) is designed. Benefitting from the abundant polar terminal groups on the MXene surface, Sn2+ is induced into the interlayer of MXene with large interlayer spacing, which is selenized in situ to obtain LBL-SnSe2 @MXene. In the heterostructure, SnSe2 layers and MXene layers are uniformly intercalated in each other, superior to other heterostructures formed by random stacking. As an anode for lithium-ion batteries, the LBL-SnSe2 @MXene is revealed to possess strong lithium adsorption ability, the small activation energy for lithium diffusion, and excellent structure stability, thus achieving outstanding electrochemical performance, especially with high specific capacities (1311 and 839 mAh g-1 for initial discharge and charge respectively) and ultralong cycling stability (410 mAh g-1 at 5C even after 16 000 cycles). This work conveys an inspiration for the controllable design and construction of homogeneous layered heterostructures.

14.
J Hepatocell Carcinoma ; 10: 43-55, 2023.
Article in English | MEDLINE | ID: mdl-36660412

ABSTRACT

Purpose: In this study, we developed a nomogram based on the platelet-albumin-bilirubin (PALBI) score to predict recurrence-free survival (RFS) after curative resection in alpha-fetoprotein (AFP)-negative (≤20 ng/mL) hepatocellular carcinoma (HCC) patients. Patients and Methods: A total of 194 pathologically confirmed AFP-negative HCC patients were retrospectively analyzed. Univariate and multivariate Cox regression analyses were performed to screen the independent risk factors associated with RFS, and a nomogram prediction model for RFS was established according to the independent risk factors. The receiver operating characteristic (ROC) curve and the C-index were used to evaluate the accuracy and the efficacy of the model prediction. The correction curve was used to assess the calibration of the prediction model, and decision curve analysis was performed to evaluate the clinical application value of the prediction model. Results: PALBI score, MVI, and tumor size were independent risk factors for postoperative tumor recurrence (P < 0.05). A nomogram prediction model based on the independent predictive factors was developed to predict RFS, and it achieved a good C-index of 0.704 with an area under the ROC curve of 0.661 and the sensitivity was 73.2%. Patients with AFP-negative HCC could be divided into the high-risk group or the low-risk group by the risk score calculated by the nomogram, and there was a significant difference in RFS between the two groups (P < 0.05). Decision curve analysis (DCA) showed that the nomogram increased the net benefit in predicting the recurrence of AFP-negative HCC and exhibited a wider range of threshold probabilities than the independent risk factors (PALBI score, MVI, and tumor size) by risk stratification. Conclusion: The nomogram based on the PALBI score can predict RFS after curative resection in AFP-negative HCC patients and can help clinicians to screen out high-risk patients for early intervention.

15.
Anal Chem ; 95(2): 1703-1709, 2023 Jan 17.
Article in English | MEDLINE | ID: mdl-36583685

ABSTRACT

Disclosing the roles of reactive sites at catalytic interfaces is of paramount importance for understanding the reaction mechanism. However, due to the difficulties in the detection of reaction intermediates in the complex heterophase reaction system, disentangling the highly convolved roles of different surface atoms remains challenging. Herein, we used CoOx as a model catalyst to study the synergy of CoTd2+ and CoOh3+ active sites in the electrocatalytic oxygen evolution reaction (OER). The formation and evolution of reaction intermediates on the catalyst surface during the OER process were investigated by in situ surface-enhanced Raman spectroscopy (SERS). According to the SERS results in ion-substitution experiments, CoOh3+ is the catalytic site for the conversion of OH- to O-O- intermediate species (1140-1180 cm-1). CoOOH (503 cm-1) and CoO2 (560 cm-1) active centers generated during the OER, at the original CoTd2+ sites of CoOx, eventually serve as the O2 release sites (conversion of O-O- intermediate to O2). The mechanism was further confirmed on Co2+-Co3+ layered double hydroxides (LDHs), where an optimal ratio of 1:1.2 (Co2+/Co3+) is required to balance O-O- generation and O2 release. This work highlights the synergistic role of metal atoms at different valence statuses in water oxidation and sheds light on surface component engineering for the rational design of high-performance heterogeneous catalysts.

17.
Front Immunol ; 13: 998236, 2022.
Article in English | MEDLINE | ID: mdl-36110851

ABSTRACT

Background: Copper ions are essential for cellular physiology. Cuproptosis is a novel method of copper-dependent cell death, and the cuproptosis-based signature for glioma remains less studied. Methods: Several glioma datasets with clinicopathological information were collected from TCGA, GEO and CGGA. Robust Multichip Average (RMA) algorithm was used for background correction and normalization, cuproptosis-related genes (CRGs) were then collected. The TCGA-glioma cohort was clustered using ConsensusClusterPlus. Univariate Cox regression analysis and the Random Survival Forest model were performed on the differentially expressed genes to identify prognostic genes. The cuproptosis-signature was constructed by calculating CuproptosisScore using Multivariate Cox regression analysis. Differences in terms of genomic mutation, tumor microenvironment, and enrichment pathways were evaluated between high- or low-CuproptosisScore. Furthermore, drug response prediction was carried out utilizing pRRophetic. Results: Two subclusters based on CRGs were identified. Patients in cluster2 had better clinical outcomes. The cuproptosis-signature was constructed based on CuproptosisScore. Patients with higher CuproptosisScore had higher WHO grades and worse prognosis, while patients with lower grades were more likely to develop IDH mutations or MGMT methylation. Univariate and Multivariate Cox regression analysis demonstrated CuproptosisScore was an independent prognostic factor. The accuracy of the signature in prognostic prediction was further confirmed in 11 external validation datasets. In groups with high-CuproptosisScore, PIK3CA, MUC16, NF1, TTN, TP53, PTEN, and EGFR showed high mutation frequency. IDH1, TP53, ATRX, CIC, and FUBP1 demonstrated high mutation frequency in low-CuproptosisScore group. The level of immune infiltration increased as CuproptosisScore increased. SubMap analysis revealed patients with high-CuproptosisScore may respond to anti-PD-1 therapy. The IC50 values of Bexarotene, Bicalutamide, Bortezomib, and Cytarabine were lower in the high-CuproptosisScore group than those in the low-CuproptosisScore group. Finally, the importance of IGFBP2 in TCGA-glioma cohort was confirmed. Conclusion: The current study revealed the novel cuproptosis-based signature might help predict the prognosis, biological features, and appropriate treatment for patients with glioma.


Subject(s)
Brain Neoplasms , Glioma , Humans , Bexarotene , Bortezomib , Brain Neoplasms/genetics , Brain Neoplasms/pathology , Class I Phosphatidylinositol 3-Kinases/genetics , Copper , Cytarabine , DNA-Binding Proteins/genetics , ErbB Receptors/genetics , Gene Expression Regulation, Neoplastic , Glioma/genetics , Glioma/pathology , Prognosis , RNA-Binding Proteins/genetics , Tumor Microenvironment/genetics , Apoptosis
18.
Am J Cancer Res ; 12(8): 3843-3856, 2022.
Article in English | MEDLINE | ID: mdl-36119821

ABSTRACT

Cathepsin A (CTSA) is overexpressed in various types of cancer and is linked to poor clinical outcomes. However, the clinical application of CTSA in HCC has not been explored. In this study, we examined the protein level of CTSA in the archived HCC samples from 161 patients by Immunohistochemistry (IHC). The high protein level of CTSA was significantly correlated to the poor clinicopathological parameters, such as TNM stage, serum AFP level, tumor differentiation, liver cirrhosis, Child-Pugh class, vascular invasion, tumor encapsulation, tumor recurrence, and patient death. In addition, multivariate Cox regression analysis indicated that high CTSA expression was an independent prognostic factor of OS and RFS. We also analyzed the area under the curve (AUC) of the time-dependent receiver operating characteristic (ROC) of CTSA expression for 1-, 3-, and 5-year OS and RFS prediction. Furthermore, we constructed a nomogram that exhibited excellent prediction performance, which was validated by the calibration curve and decision curve analysis. Together, our study demonstrated that CTSA protein level is strongly associated with poor clinical outcome of HCC patients and may be used as a potential diagnostic and prognostic biomarker in HCC.

19.
Article in English | MEDLINE | ID: mdl-35830499

ABSTRACT

Improving dissociation and diffusion of lithium ions is the key to solving the practical application of polymer-based solid-state electrolytes (SSE). Here, a low-cost three-dimensional hydroxyapatite (HAP) nanowire is used in polyethene oxide to obtain an enhanced lithium-ion electrolyte. The oxygen-rich interface of HAP provides an integrated dissociation-diffusion platform for lithium salts. The TFSI- anions tend to coordinate with calcium ions, which makes it easier for lithium ions to escape and stay in a free state. The lateral nucleus in the HAP polyethene electrolyte regulates the diffusion from spherical diffusion into linear planar diffusion, which is confirmed by chronoamperometry curves and in situ observation. The stability of the electrolyte at high voltages is improved by inhibiting the superoxide radicals of polyethene oxide chains, which is demonstrated by nuclear magnetic resonance and electron paramagnetic resonance spectroscopy methods. The initial specific charge capacity of the Li/SPE/LiFePO4 cell with HAP-modified polyethene oxide at 2 C is 148.8 mA h/g, and its initial Coulombic efficiency is 95.17%. After 100 cycles, the specific discharge capacity is 125.5 mA h/g with 99.91% retention per cycle. This oxygen-rich interface strategy would guide the discovery of novel materials for polymer-based SSE.

20.
Am J Cancer Res ; 12(5): 1995-2011, 2022.
Article in English | MEDLINE | ID: mdl-35693077

ABSTRACT

High recurrence rate in HCC is the primary cause of the poor prognosis after hepatectomy. Therefore, in this study, we aimed to construct a gene signature for predicting the recurrence rate in HCC. The mRNA expression profiles and clinical information of HCC patients from GEO and TCGA databases were used, and ferroptosis-related gene list was obtained from the FerrDb database. We identified 39 ferroptosis-related genes (FDEGs) that were differentially expressed between HCC samples and normal tissues from the GSE14520 dataset. The univariate and multivariate Cox regression analyses were employed to construct a prognostic signature. Seven FDEGs (MAPK9, SLC1A4, PCK2, ACSL3, STMN1, CDO1, and CXCL2) were included to construct a risk model, which was validated in the TCGA dataset. Patients in high-risk groups exhibited a significantly poor prognosis compared with patients in low-risk groups in both the training set (GSE14520 cohort) and the validation set (TCGA cohort). Multivariate cox regression analyses demonstrated that the 7-gene signature was an independent risk factor for RFS in HCC patients. KEGG analysis showed that FDEGs were mainly enriched in Ferroptosis, Hepatocellular carcinoma pathway, and MAPK signaling pathway. GSEA analysis suggested that the high-risk group was correlated with multiple oncogenic signatures and invasive-related pathways. These results indicated that this risk model can accurately predict recurrence after hepatectomy and offer novel research directions for personalized treatment in HCC patients.

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