The exploration of inexpensive, facile, and large‐scale methods to prepare carbon scaffolds for high sulfur loadings is crucial for the advancement of Li–S batteries (LSBs). Herein, the authors report a new nitrogen and oxygen in situ dual‐doped nonporous carbonaceous material (NONPCM) that is composed of a myriad of graphene‐analogous particles. Importantly, NONPCM could be fabricated on a kilogram scale via inexpensive and green hydrothermal‐carbonization‐combined methods. Many active sites on the NONPCM surface are accessible for the efficient surface‐chemistry confinement of guest sulfur and its discharge product; this confinement is exclusive of physical entrapment, considering the low surface area. Electrochemical examination demonstrates excellent cycle stability and rate performance of the NONPCM (K)/S composite, even with a sulfur loading of 80 or 90 wt%. Hence, the scaffolds for LSBs exhibit potential for industrialization through further optimization and expansion of the present synthesis.
Well-distributed graphene sheets doped with nitrogen (NGS) were prepared via a thermal annealing strategy with the existence of cyanamide. The cyanamide can efficiently restrain the conglomeration of the resultant graphene sheets and synchronously make sure the doping of nitrogen. Followed by the next-step of low-temperature solvothermal route, uniform ultrasmall tin sulfide (SnS 2 ) nanocrystals were readily grown on the preformed NGS (denoted as SnS 2 -NGS).Benefiting from the synergistic function between NGS and SnS 2 , the resultant composites exhibit excellent electrochemical performance. In case of estimation as anode materials for lithium-ion batteries (LIBs), SnS 2 -NGS with moderate weight ratio of SnS 2 deliver outstanding electrochemical outcomes giving the high reversible capacity of 1407 mA h g -1 at 200 mA g -1 after 120 cycles. The composites can also maintain a reversible capacity of about 200 mA h g -1 at a high current density of 10 A g -1 . The lithium-ion storage ability of prepared SnS 2 -NGS electrode is at the top rank in comparison with the other works. The obtained composites also achieve good sodium storage ability.
Herein, we have designed and first synthesized a unique ternary hybrid structure by simultaneously growing SnS and MoS particles on graphene sheets (denoted as MoS/SnS-GS) via one-pot hydrothermal route. The charge incompatibility between MoO and graphene oxide with negative charged functional groups on surface can be compromised with the aid of Sn cations, which renders the final formation of SnS and MoS on GS surface. This is the first report of the cohybridization of MoS and SnS with GS matrix from anionic and cationic precursors in the absence of premedication of graphene surface. When MoS/SnS-GS acts as anodes for lithium-ion batteries, the hybrids exhibit much better cycling stability than MoS-GS and SnS-GS counterparts. The compact adhesion of MoS/SnS nanoparticles helps offset the undesired result of destruction of electrode materials resulting from volume expansion during repeated cycles. Furthermore, by combination with their synergetic effect on interface and the presence of discrepant asynchronous electrochemical reactions for SnS and MoS, MoS/SnS-GS hybrids are endowed with improvement of electrochemical capabilities. Besides, they also showed outstanding Na-storage ability.
Chalcogenide micro/nanocomposite structures have been attracting worldwide attention due to prospective applications in photocatalytic hydrogen production. Well-defined micro/nanostructures with pronounced properties are of extraordinary importance. Herein, a facile one-pot method for the synthesis of monodisperse, size-controllable CdS core-shell and CdS@Zn Cd S core-double shell submicrospheres, which were engineered with respect to structure and size, is reported. CdS core-shell submicrospheres with different sizes were selectively prepared for the first time. The growth mechanism was investigated in detail by monitoring the time-dependent morphology of intermediates by TEM. By introduction of a zinc precursor in the synthetic system, CdS@Zn Cd S core-double shell submicrospheres were obtained by cation exchange of CdS with zinc ions, with a process of diffusion of CdS towards the outside and transformation of Zn Cd S crystallites. The H evolution rate over CdS@Cd Zn S (5.17 mmol h g ) is 12.3 times that of CdS core-shell structures (0.42 mmol h g ) under visible light, owing to the efficient charge separation, as demonstrated by electrochemical impedance and transient-state time-resolved photoluminescence spectroscopy. Furthermore, CdS@Zn Cd S core-double shell structures exhibited excellent stability over 20 h of hydrogen production.
Tumor-infiltrating T-lymphocytes are defined as T-lymphocytes that infiltrated into tumor tissues; however, their composition, clinical significance, and underlying mechanism in hepatocellular carcinoma (HCC) and adjacent non-tumor tissues are still not completely understood. Herein, we collected marker genes of T cell subpopulations from a previous study and estimated their relative infiltrating levels in HCC and adjacent non-tumor tissues. Specifically, the infiltrating levels of all the T cells were significantly reduced in HCC as compared with non-tumor tissues. Unsupervised clustering of the HCC samples by the T cell infiltrating levels revealed that the HCC samples could be clearly classified into two groups. The driver genes, including PTK2B , ATM , PIK3C2B , and KIT , and several CNAs were observed to be associated with reduced T cell infiltrating levels. Particularly, deletion of TP53 more frequently occurred in low T cell infiltration HCC samples and resulted in its downregulation and cell cycle progression, indicating that cell cycle progression was closely associated with reduced T cell infiltration. In contrast, for the samples with high infiltration T cells, its immune evasion might be regulated by the immune checkpoint regulators, such as PD-1/PD-L1 and CTLA4. Moreover, Olaparib, one of the PARP inhibitors, and immune checkpoint inhibitors might be therapeutic candidates for the samples from the two T cell infiltrating clusters. Clinically, the tumor-infiltrating levels of cytotoxic CD4 cell, Mucosal associated invariant T (MAIT) cell, and exhausted CD8 + T cell might be used as predictors for vascular invasion, recurrence, and overall survival. Collectively, we systematically evaluated the clinical significance and potential molecular mechanisms of tumor-infiltrating T cell subpopulations in hepatocellular carcinoma, which might broaden our insights into the immunological features of HCC and provide potential immunotherapeutic targets.
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