RESUMEN
A novel heterotrinuclear complex [Cu2(L)Na(µ-NO3)]âCH3OHâCHCl3 derived from a symmetric bis(salamo)-type tetraoxime H4L having a naphthalenediol unit, was prepared and structurally characterized via means of elemental analyses, UV-Vis, FT-IR, fluorescent spectra and single-crystal X-ray diffraction. The heterobimetallic Cu(II)â»Na(I) complex was acquired via the reaction of H4L with 2 equivalents of Cu(NO3)2·2H2O and 1 equivalent of NaOAc. Clearly, the heterotrinuclear Cu(II)â»Na(I) complex has a 1:2:1 ligand-to-metal (Cu(II) and Na(I)) ratio. X-ray diffraction results exhibited the different geometric behaviors of the Na(I) and Cu(II) atoms in the heterotrinuclear complex; the both Cu(II) atoms are sited in the N2O2 coordination environments of fully deprotonated (L)4− unit. One Cu(II) atom (Cu1) is five-coordinated and possesses a geometry of slightly distorted square pyramid, while another Cu(II) atom (Cu2) is four-coordination possessing a square planar coordination geometry. Moreover, the Na(I) atom is in the O6 cavity and adopts seven-coordination with a geometry of slightly distorted single triangular prism. In addition, there are abundant supramolecular interactions in the Cu(II)â»Na(I) complex. The fluorescence spectra showed the Cu(II)â»Na(I) complex possesses a significant fluorescent quenching and exhibited a hypsochromic-shift compared with the ligand H4L.
Asunto(s)
Complejos de Coordinación/síntesis química , Cobre/química , Sodio/química , Complejos de Coordinación/química , Cristalografía por Rayos X , Modelos Moleculares , Estructura Molecular , Oximas/química , Espectrometría de FluorescenciaRESUMEN
Human tongue squamous cell carcinoma (TSCC), the most prevalent type of oral cancer, is associated with human papillomavirus (HPV) infection. Our previous work showed Karyopherin α2 (KPNA2), as an oncogene of TSCC, by relegating the p53/autophagy signaling pathway. Nevertheless, the significance of KPNA2 in TSCC pathogenesis has not been established. KPNA2 levels were evaluated via the TCGA database, and its effects on survival outcomes were assessed by LASSO, Kaplan-Meier, and COX regression analyses. CIBERSORT and ESTIMATE investigated the relationships between KPNA2 and immune infiltration. At the same time, KPNA2 and HPV infection was analyzed by immunohistochemistry. In addition, the association between downstream molecular regulation pathways and KPNA2 levels was determined by GO, GSEA, and WGCNA. In TSCC, KPNA2 levels were associated with clinical prognosis and tumor grade. Moreover, KPNA2 may be involved in cancer cell differentiation and facilitates tumor-related genes and signaling pathways, such as Cell Cycle, Mitotic G1 phase, G1/S transition, DNA Repair, and Transcriptional Regulation TP53 signaling pathways. Nevertheless, regulatory B cells, follicular helper B cells, and immune and stromal scores between low- and high-KPNA2 expression groups were insignificant. These results imply that KPNA2 is highly involved in tumor grade and prognosis of TSCC. KPNA2 levels correct with HPV 16 markedly regulated cell differentiation, several oncogenes, and cancer-related pathways.
RESUMEN
A newly synthesized fluorescent chemosensor H6L was explored for detecting B4O72-, characterized by 1H NMR spectrum, mass spectrum and fluorescence spectra. During the detection process of B4O72-, the fluorescence is significantly enhanced and naked eye recognition can be performed under 365 nm UV light without any interference by other typical anions. The limit of detection is as low as 6.97 × 10-10 M. In addition, in order to broaden the application of salamo-based fluorescence sensors in the field of biology, except for the fluorescence imaging of HeLa cells, the first attempt of exogenous detection in zebrafish was conducted successfully.
Asunto(s)
Colorantes Fluorescentes , Pez Cebra , Animales , Aniones , Células HeLa , Humanos , Espectrometría de FluorescenciaRESUMEN
A new sensor H5L for continuous identification of Cu2+, Al3+ and lysine was synthesized by Schiff base reactions. The sensor could specifically recognized Cu2+ in the EtOH/H2O (1:1 v/v) solution by UV-vis spectra, and the binding constant with Cu2+ can reach 1011â¯M-1, meanwhile, it was found by the naked-eye that the color of the solution was changed from colorless to yellow. The copper complex L-Cu2+ formed by the sensor H5L and Cu2+ could further recognize Al3+ and lysine in the fluorescence spectra. The LOD values of the three objects were 2.67â¯×â¯10-8, 1.96â¯×â¯10-8 and 5.59â¯×â¯10-9â¯M, respectively. In addition, fluorescence intracellular images of Al3+ and lysine were performed and obtained satisfactory results.
Asunto(s)
Colorantes Fluorescentes , Bases de Schiff , Cobre , Espectrometría de FluorescenciaRESUMEN
Two salamo-like copper(II) complex probes, L1-Cu2+ and L2-Cu2+, were designed and synthesized for sensitive and efficient identification of CN-. UV spectroscopy, high resolution mass spectrometry, RGB analysis and naked eye recognition were performed to explore their recognition mechanisms. High resolution mass spectra indicated that the probes L1-Cu2+ and L2-Cu2+ formed complexes with CN-. The two probes could recognize CN- by the naked eye and the color of the solution changed from light yellow to red. In terms of application, the contents of CN- in the environmental water samples were tested. In addition, the optimal pH ranges for probe detection of CN- were investigated by pH value measurement.
RESUMEN
In this paper, a salamo-based copper(ii) complex probe L-Cu2+ was synthesized, which combined with copper(ii) ions to form L-Cu2+ for the detection of S2- and had a good fluorescence chemical response. Through spectral analysis, we found that S2- could be identified with high sensitivity and selectivity in the presence of various anions and could be used for the detection of S2- by the naked eye. With the addition of S2-, the solution color changed from colorless to bright yellow. UV absorption, fluorescence and other characterization methods were carried out, and the mechanism of action was determined. In addition, we performed a visual inspection of H2S gas, and the probe L-Cu2+ could detect S2- in the gas molecules, revealing its potential application value in biology and medicine.
RESUMEN
Four homo/heterometallic complexes [Cu3(L)(µ2-OAc)9(CH3OH) 9]·3CHCl3 (1), [Cu2(L)Ca(µ2-NO3)9] (9), [{Cu2(L)Sr(µ2-NO3)9}9]·CH3CH2OH (11) and [Cu2(L)Ba(µ2-OAc)9(OAc)] (14), containing an acyclic naphthalenediol-based ligand H4L, were synthesized and characterized by elemental analyses, IR, UV-Vis, fluorescence spectra, TG-DTA and X-ray crystallography. The complex 1 was obtained by the reaction of H4L with 11 equivalents of Cu(OAc) 9·2H2O. The heterometallic complexes 9, 11, 14 were acquired by the reaction of H4L with 9 equivalents of Cu(OAc)9·2H2O or Cu(NO3)9·2H2O and 1 equivalent of M(OAc)9 (Mâ¯=â¯Ca, Sr and Ba). Owing to the different coordination cavities of the N2O2 and O6 of the completely deprotonated (L)14- unit, the crystal structures showed the N2O2 sites were occupied by Cu(II) atoms, alkaline earth metal(II) atoms occupied the O6 site of the ligand (L)14- unit, respectively. Furthermore, the fluorescence properties and TG-DTA analyses were discussed.