A Highly Luminescent Chiral Tetrahedral Eu₄L₄(L′)₄ Cage: Chirality Induction, Chirality Memory, and Circularly Polarized Luminescence

Chiral lanthanide cages with circularly polarized luminescence (CPL) properties have found potential application in enantioselective guest recognition and sensing. However, it still remains a big challenge to develop a simple and robust method for the diastereoselective assembly of homochiral lanthanide cages in view of the large lability of the Ln­(III) ions. Herein, we report the first example of the formation of a enantiopure lanthanide tetrahedral cage via a chiral ancillary ligand induction strategy. One such cage, (Eu4L4)­(R/S-BINAPO)4, is assembled by four achiral C3-symmeric tris­(β-diketones) (4,4′,4″-tris­(4,4,4-trifluoro-1,3-dioxobutyl)­triphenylamine, L) as faces, four Eu­(III) ions as vertices and four chiral R-/S-bis­(diphenylphosphoryl)-1,1′-binaphthyl (R/S-BINAPO) as ancillary ligands. X-ray crystallography and NMR and CD spectra confirm the formation of a pair of enantiopure chiral topological tetrahedral cages, (Eu4L4)­(R-BINAPO)4 and (Eu4L4)­(S-BINAPO)4 (ΔΔΔΔ-1 and ΛΛΛΛ-1). As expected, the tetrahedral cages present strong CPL with |glum| values up to 0.20, while they unexpectedly give ultrahigh luminescent quantum yields (QYs) of up to 81%, the highest value reported in chiral Ln­(III) complexes. More impressively, the chiral memory effect for a lanthanide-based assembly is observed for the first time. The chirality of the original cage 1 framework is retained after R/S-BINAPO is replaced by the achiral bis­[2-(diphenylphosphino)­phenyl] ether oxide (DPEPO), and thus another pair of enantiopure Eu­(III) tetrahedral cages, ΔΔΔΔ- and ΛΛΛΛ-[(Eu4L4)­(DPEPO)4] (ΔΔΔΔ-2 and ΛΛΛΛ-2), have been isolated. Encouragingly, cage 2 also presents an impressive luminescence quantum yield (QY = 68%) and intense CPL (|glum| = 0.11). This study offers a simple and low-cost synthesis strategy for the preparation of lanthanide cages with CPL properties

Solid–Liquid Phase Equilibrium and Diagram of a l‑Phenylalanine–Hydrogen Peroxide–Water Ternary System

The equilibrium solubility data of l-phenylalanine (C9H11NO2) dissolved in hydrogen peroxide solutions with different concentrations were obtained at 273.15 and 283.15 K by the use of a static method under ambient pressure (p = 101.2 kPa), and the ternary phase diagrams of the C9H11NO2–H2O2–H2O system were constructed according to the determined solubility. At 273.15 and 283.15 K, two neat solid phases were generated in the ternary C9H11NO2–H2O2–H2O system, which corresponded to C9H11NO2 and l-phenylalanine perhydrate C9H11NO2·H2O2·0.5H2O. The adduct C9H11NO2·H2O2·0.5H2O was identified by the traditional method of Schreinemaker’s wet residue. The solubilities of C9H11NO2 and C9H11NO2·H2O2·0.5H2O in water slightly increased with a rise in temperature. The crystalline region of the adduct of C9H11NO2·H2O2·0.5H2O shrunk as the experimentation temperature increased, indicating a little effect of temperature on the yield of C9H11NO2·H2O2·0.5H2O. Finally, the effect of ethanol and sodium chloride on the phase equilibrium was studied. Adding a certain amount of ethanol and sodium chloride can reduce the solubility of l-phenylalanine

Eu(III) Tetrahedron Cage as a Luminescent Chemosensor for Rapidly Reversible and Turn-On Detection of Volatile Amine/NH₃

Because of the involvement of the gas–solid diffusion, device fabrication, and the relatively complex photophysical process, the lanthanide complexes are rarely exploited as fluorescence sensors for volatile compound (VC) detection. Herein, we report the first example of a discrete 3D Ln-based architecture as a sensor for VCs. The designed Eu4L4 tetrahedral cage shows highly selective, rapidly reversible, and turn-on emissive responses toward volatile amines/NH3 in a spin-coated film. Through the comprehensive spectral characteristic and density functional theory calculation, an intermolecular weak nucleophilic interaction is proposed for this response mechanism. Combining this weak interactions with the permeability of the cage, the film presents subsecond to second timescales rapid response; combining the fitting electrophilic capability of the β-diketonate units to amine nitrogen with the tunable intramolecular charge-transfer feature, the cage shows excellent selectivity and turn-on emissive response. This work provides a new clue to develop the lanthanide complexes as luminescence probes for VCs

The Cold-Inducible RNA-Binding Protein (CIRP) Level in Peripheral Blood Predicts Sepsis Outcome

<div><p>Objectives</p><p>Sepsis is a lethal and complex clinical syndrome caused by infection or suspected infection. Cold-inducible RNA-binding protein (CIRP) is a widely distributed cold-shock protein that plays a proinflammatory role in sepsis and that may induce organ damage. However, clinical studies regarding the use of CIRP for the prognostic evaluation of sepsis are lacking. The purpose of this research was to investigate the prognostic significance of peripheral blood concentrations of CIRP in sepsis. Sepsis was assessed using several common measures, including the Acute Physiology and Chronic Health Evaluation II (APACHE II) score; the Sepsis-related Organ Failure Assessment (SOFA) score; the lactate, serum creatinine, and procalcitonin (PCT) levels; the white blood cell (WBC) count; and the neutrophil ratio (N%).</p><p>Design</p><p>Sixty-nine adult patients with sepsis were enrolled in this study. According to the mortality data from the hospital, 38 patients were survivors, and 31 were nonsurvivors. The plasma levels of the biomarkers were measured and the APACHE II and SOFA scores were calculated within 24 hours of patient enrollment into our study. The CIRP level was measured via ELISA.</p><p>Results</p><p>The plasma level of CIRP was significantly higher in the nonsurvivors than in the survivors (median (IQR) 4.99 (2.37–30.17) ng/mL and 1.68 (1.41–13.90) ng/mL, respectively; <i>p</i> = 0.013). The correlations of the CIRP level with the APACHE II score (r = 0.248, <i>p</i> = 0.040, n = 69), the SOFA score (r = 0.323, <i>p</i> = 0.007, n = 69), the serum creatinine level (r = 0.316, <i>p</i> = 0.008, n = 69), and the PCT level (r = 0.282, <i>p</i> = 0.019, n = 69) were significant. Receiver operator characteristic (ROC) curve analysis showed that the area under the ROC curve (AUC) for the CIRP level was 0.674 (<i>p</i> = 0.013). According to Cox proportional hazards models, the CIRP level independently predicts sepsis mortality. When the CIRP level in the peripheral blood increased by 10 ng/mL, the mortality risk increased by 1.05-fold (<i>p</i> = 0.012). Thus, the CIRP level reflects the degree of renal injury but does not predict the severity of sepsis or organ damage.</p><p>Conclusion</p><p>An elevated plasma concentration of CIRP was significantly associated with poor prognosis among patients with sepsis. Therefore, CIRP is a potential predictor of sepsis prognosis.</p></div

Eu(III) Tetrahedron Cage as a Luminescent Chemosensor for Rapidly Reversible and Turn-On Detection of Volatile Amine/NH₃

Because of the involvement of the gas–solid diffusion, device fabrication, and the relatively complex photophysical process, the lanthanide complexes are rarely exploited as fluorescence sensors for volatile compound (VC) detection. Herein, we report the first example of a discrete 3D Ln-based architecture as a sensor for VCs. The designed Eu4L4 tetrahedral cage shows highly selective, rapidly reversible, and turn-on emissive responses toward volatile amines/NH3 in a spin-coated film. Through the comprehensive spectral characteristic and density functional theory calculation, an intermolecular weak nucleophilic interaction is proposed for this response mechanism. Combining this weak interactions with the permeability of the cage, the film presents subsecond to second timescales rapid response; combining the fitting electrophilic capability of the β-diketonate units to amine nitrogen with the tunable intramolecular charge-transfer feature, the cage shows excellent selectivity and turn-on emissive response. This work provides a new clue to develop the lanthanide complexes as luminescence probes for VCs

Areas under the receiver operating characteristic curves for certain biomarker levels and the severity scores in the prediction of sepsis severity and organ failure in patients with sepsis.

<p>*<i>p-</i>value ≦ 0.05</p><p>**<i>p-</i>value ≦ 0.01</p><p>Areas under the receiver operating characteristic curves for certain biomarker levels and the severity scores in the prediction of sepsis severity and organ failure in patients with sepsis.</p

Eu(III) Tetrahedron Cage as a Luminescent Chemosensor for Rapidly Reversible and Turn-On Detection of Volatile Amine/NH₃

Because of the involvement of the gas–solid diffusion, device fabrication, and the relatively complex photophysical process, the lanthanide complexes are rarely exploited as fluorescence sensors for volatile compound (VC) detection. Herein, we report the first example of a discrete 3D Ln-based architecture as a sensor for VCs. The designed Eu4L4 tetrahedral cage shows highly selective, rapidly reversible, and turn-on emissive responses toward volatile amines/NH3 in a spin-coated film. Through the comprehensive spectral characteristic and density functional theory calculation, an intermolecular weak nucleophilic interaction is proposed for this response mechanism. Combining this weak interactions with the permeability of the cage, the film presents subsecond to second timescales rapid response; combining the fitting electrophilic capability of the β-diketonate units to amine nitrogen with the tunable intramolecular charge-transfer feature, the cage shows excellent selectivity and turn-on emissive response. This work provides a new clue to develop the lanthanide complexes as luminescence probes for VCs

Correlations between the CIRP level and the levels of other biomarkers.

<p>The correlations of the plasma CIRP level with the APACHE II score; the SOFA score; the serum lactate, creatinine, and procalcitonin (PCT) levels; the white blood cell (WBC) count; and the neutrophil ratio (N%) were determined in the 69 patients with sepsis (Spearman rank analysis). <i>r</i> represents Spearman’s correlation coefficient, and a <i>p-</i>value < 0.05 was considered to be statistically significant.</p

Comparison of the plasma biomarker levels between the survivors and nonsurvivors of sepsis.

<p>CIRP = cold-inducible RNA-binding protein, WBC = white blood cell, N% = neutrophil ratio, PCT = procalcitonin.</p><p>The <i>p-</i>values for these biomarkers were obtained using the Mann-Whitney <i>U</i> test. A <i>p</i>-value < 0.05 was considered to be statistically significant.</p><p>IQR = inter-quartile range, SD = standard deviation.</p><p>Comparison of the plasma biomarker levels between the survivors and nonsurvivors of sepsis.</p