A convenient nanoscale technique is reported for the fabrication of highly ordered hemispherical silver nanocap arrays templated by porous anodic alumina (PAA) membranes as robust and cost-efficient surface-enhanced Raman scattering (SERS) substrates. This geometry produces a high Raman signal due to its periodic hexagonal arrangements and control of the gap between the nanostructures in the sub-10-nm regime. The surface structure can be tuned further to optimize the enhancement factor according to optional PAA fabrication and silver deposition parameters. Finite-difference time-domain calculations indicate that the structure may possess excellent SERS characteristics due to the high density and abundance of hot spots.
Background: Tumor IL17-producing (IL17A þ) cells infiltration has different prognostic values among various cancers. The objective of this study was to assess the effect of IL17A þ cells in gastric cancer. Patients and methods: The study included two patient cohorts, the Cancer Genome Atlas cohort (TCGA, n ¼ 351) and the Zhongshan Hospital cohort (ZSHC, n ¼ 458). The TCGA and ZSHC were used for mRNA-related and cells infiltration-related analyses, respectively. The roles of IL17A mRNA and IL17A þ cells in overall survival (OS), response to adjuvant chemotherapy (ACT), and immune contexture were evaluated. Another independent cohort was included to identify the correlation between mRNA of IL17A and IL17A þ cells infiltration (the preliminary Zhongshan Hospital cohort, PZSHC, n ¼ 21). Results: The infiltration of IL17A þ cells was positively correlated with the expression of IL17A mRNA (Spearman's q ¼ 0.811; P < 0.001). High IL17A mRNA expression and intratumoral IL17A þ cells were correlated with improved OS and remained to be significant after adjusted for confounders. Patients with TNM II/III disease whose tumor present higher intratumoral IL17A þ cells or lower peritumoral IL17A þ cells can benefit more from ACT. Elevated IL17A mRNA expression and increased intratumoral IL17A þ cells infiltration was associated with more antitumor mast cells and nature killer cells infiltration and less pro-tumor M2 macrophages infiltration. High IL17A mRNA expression represented a Th17 cells signature and immune response process and was correlated with increased cytotoxic GZMA, GZMB, IFNG, PRF1, and TNFSF11 expression. Conclusions: IL17A mRNA expression and intratumoral IL17A þ cells infiltration were correlated with antitumor immune contexture. IL17A þ cells infiltration could be used as an independent prognostic biomarker for OS and predictive biomarker for superior response to ACT, and further prospective validation needs to be conducted.
The shuttle effect of polysulfide (Li 2 S n , 2 < n ≤ 8) and the sluggish reaction kinetics seriously hinder the development of lithium−sulfur (Li−S) batteries. Regulating the electronic structure of substrate materials could be an effective strategy to further modulate surface polysulfide adsorption and interface electron transfer for advanced Li−S batteries. Herein, a cobalt-doped vanadium nitride (Co-VN) microflower hierarchical structure with a 5% Co/V ratio was synthesized as a substrate material. Theoretical calculation indicated that the polysulfide adsorption energy of Co-VN (−5.04 eV) was enhanced compared to that of VN (−4.14 eV). Electrochemical experiments verified that the polarization and internal resistance of VN were lowed after Co doping. Electrochemical tests showed that the cyclic stability of the Co-VN/sulfur (Co-VN/S) composite cathode was greatly improved compared to the undoped one, achieving an impressive initial capacity of 706 mAh g −1 at 2.0 C and that the fading rate of discharge capacity over 500 cycles was only 0.034% per cycle. A discharge capacity of 873 mAh g −1 under remarkable sulfur loading (4.42 mg cm −2 ) was also achieved with a capacity decay rate of 0.028% per cycle over 100 cycles.
Endohedral metallofullerenes (EMFs) encapsulating divalent metal ions have received limited attention because of their low production yields. Here, we report the results of structural determination and chemical functionalization of a typical divalent metallofullerene, Yb@C84(II). Single-crystal X-ray crystallographic studies of Yb@C84/Ni(II)(OEP) cocrystals (OEP is the dianion of octaethylporphyrin) unambiguously established the chiral C2(13)-C84 cage structure and revealed multiple sites for Yb(2+), indicating a moving metal ion inside the cage. The chemical property of Yb@C2(13)-C84 was probed with the electrophillic adamantylidene carbene (1). Three monoadduct isomers were isolated and characterized. Crystallographic results of the major isomer (2b) revealed that, although the cycloaddition breaks a [5,6]-bond on the cage, Yb(2+) is localized under a hexagonal ring distant from the sites of addition. Thus, it is proved that the dynamic motion of the divalent metal ion in Yb@C84 has been effectively halted by exohedral functionalization. Spectroscopic results show that the electronic property of Yb@C2(13)-C84 is pertained in the derivatives, although the addend exerts a mild reduction effect on the electrochemical behavior of the EMF. Computational works demonstrated that addition of 1 to Yb@C2(13)-C84 is mainly driven by releasing the local strains of cage carbons rather than charge recombination, which is always prominent to the affinity of typical trivalent EMFs such as M@C2v(9)-C82 (M = Sc, Y, La, Ce, Gd) toward 1. Accordingly, it is speculated that the chemical behaviors of divalent EMFs more likely resemble those of empty fullerenes because both are closed-shell compounds, but they differ from those of trivalent EMFs, which have open-shell electronic configurations instead.
Quantitative analysis of the output of processes and molecular interactions within a single cell is highly critical to the advancement of accurate disease screening and personalized medicine. Optical detection is one of the most broadly adapted measurement methods in biological and clinical assays and serves cellular phenotyping. Recently, microfluidics has obtained increasing attention due to several advantages, such as small sample and reagent volumes, very high throughput, and accurate flow control in the spatial and temporal domains. Optofluidics, which is the attempt to integrate optics with microfluidic, shows great promise to enable on-chip phenotypic measurements with high precision, sensitivity, specificity, and simplicity. This paper reviews the most recent developments of optofluidic technologies for cellular phenotyping optical detection.
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