Artificial enzyme mimics are more stable and cost-effective than bioenzymes, but they usually lack substrate recognition function. Here, we report that uranyl (UO 2 2+ ) features efficient artificial peroxidase activity with a high specificity and can catalyze the oxidation of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium (ABTS) by H 2 O 2 to yield green ABTS radical (ABTS •+ ), whereas other common substrates such as 3,3′-diaminobenzidine (DAB), 3,3′,5,5′-tetramethylbenzidine (TMB), o-phenylenediamine (OPD), and dopamine (DA) are not oxidized. The high specificity of UO 2 2+ peroxidase mimic is ascribed to the electrostatic-driven coordination interaction between ABTS anion and UO 2 2+ cation, and the orthorhombic metastudtite from the reaction between H 2 O 2 and UO 2 2+ rather than reactive radicals is identified as the key intermediate, which accounts for ABTS oxidation. On the basis of the UO 2 2+ peroxidase mimic, a facile, low-cost, and reliable colorimetric assay is fabricated. The resulting colorimetric assay displays a good analytical performance for UO 2 2+ detection in a linear range of 10−100 μM, along with a limit of detection of 0.5 μM. Further, the present colorimetric assay has a good selectivity toward UO 2 2+ over common metal ions, which is applied for determination of UO 2 2+ in natural water samples with satisfactory recovery results.
Life is preserved by complex enzymatic reaction systems. Inspired by life, here we report on the first example to fabricate blue light-gated reversible silver nanozyme reaction networks that achieve life-like adaptivity. Upon blue light excitation, silver nanoparticles (AgNPs) display oxidase-like activity in the presence of Cl − as a cofactor. The addition of Cl − promotes the separation between hot holes and electrons that are generated by excited-state surface plasmon of AgNPs, inducing the generation of highly reactive hydroxyl and superoxide anion radicals. They oxidize colorless 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt (ABTS) to yield green ABTS radicals (ABTS •+ ). It is shown that ABTS •+ is able to be reduced by AgNPs to regenerate ABTS when the blue light is turned off, and the reaction system returns to its initial state, which is the typical feature of the artificial adaptive system. The dynamic process of the adaptive system is tunable by changing the concentrations of AgNPs and Cl − , and it possesses excellent recyclable performance, which can be repeated at least six times. Overall, the silver nanozyme reaction networks are capable of responding to blue light stimuli and renewing by recycling to the initial state without blue light irradiation.
RimK-like family member B (RIMKLB) is an enzyme that post-translationally modulates ribosomal protein S6, which can affect the development of immune cells. Some studies have suggested its role in tumor progression. However, the relationships among RIMKLB expression, survival outcomes, and tumor-infiltrating immune cells (TIICs) in colorectal cancer (CRC) are still unknown. Therefore, we analyzed RIMKLB expression levels in CRC and normal tissues and investigated the correlations between RIMKLB and TIICs as well as the impact of RIMKLB expression on clinical prognosis in CRC using multiple databases, including the Tumor Immune Estimation Resource (TIMER), Gene Expression Profiling Interactive Analysis (GEPIA), PrognoScan, and UALCAN databases. Enrichment analysis was conducted with the cluster Profiler package in R software to explore the RIMKLB-related biological processes involved in CRC. The RIMKLB expression was significantly decreased in CRC compared to normal tissues, and correlated with histology, stage, lymphatic metastasis, and tumor status (p < 0.05). Patients with CRC with high expression of RIMKLB showed poorer overall survival (OS) (HR = 2.5,p = 0.00,042), and inferior disease-free survival (DFS) (HR = 1.9,p = 0.19) than those with low expression of RIMKLB. TIMER analysis indicated that RIMKLB transcription was closely related with several TIICs, including CD4+ and CD8+ T cells, B cells, tumor-associated macrophages (TAMs), monocytes, neutrophils, natural killer cells, dendritic cells, and subsets of T cells. Moreover, the expression of RIMKLB showed significant positive correlations with infiltrating levels of PD1 (r = 0.223, p = 1.31e-06; r = 0.249, p = 1.25e-03), PDL1 (r = 0.223, p = 6.03e-07; r = 0.41, p = 5.45e-08), and CTLA4 (r = 0.325, p = 9.68e-13; r = 0.41, p = 5.45e-08) in colon and rectum cancer, respectively. Enrichment analysis showed that the RIMKLB expression was positively related to extracellular matrix and immune inflammation-related pathways. In conclusion, RIMKLB expression is associated with survival outcomes and TIICs levels in patients with CRC, and therefore, might be a potential novel prognostic biomarker that reflects the immune infiltration status.
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