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The thermal-coupled levels (TCLs) of lanthanides have attracted great attention in the field of optical thermometer, offering an efficient method to achieve non-contect temperatuer feedback in complex environment. However, the iner 4f electrons are shielded, which becomes the core obstacle in improving the sensing performance. This issue is now circumvented by constructing an electron transfer pathway between Tm3+(1D2) and Eu3+(5D0) configurations. As a result, the electron transfer barrier is related to the relative temperature sensitivity, giving an insight into the modulation mechanism. Compared to the conventional TCLs systems, the relative temperature sensitivity of this strategy is highly concentration-responsive, increasing from 5.56 to 10.1 % K-1 as the Eu3+ molar concentration rises from 0.3 to 0.5 mol%. This work reveals the inner emission mechanism based on IVCT-supported emission mode, and presents the highly adjustability of sensing performance.
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Optical thermometers based on lanthanide thermal-coupled levels have attracted great attention owing to its fundamental importance in the fields of public health, biology, and integrated circuit. However, the inherent structural properties (shielded effect on 4f configurations, intense non-radiation relaxation) strictly suppress the sensing performance, limiting the relative temperature sensitivity (SR). To circumvent these limitations, we propose an intervalence charge transfer mashup strategy by inducing d0 electron configured transition metals. Specifically, transition metals Ta5+ is incorporated in Tm3+/Eu3+:LiNbO3, which improves the SR from 5.30 to 11.16% K-1. The validity of this component-modulation behavior is observed on other oxide crystals (NaY(Mo1-zWzO4)2) as well. Furthermore, the observed regulation is well explained by DFT calculation that indicates the d-orbit component at valence band minimum remains the core factor governing the electron transfer process. We successfully relate the SR to the band structure of luminescence carrier, offering a novel perspective for the collocation design of lanthanide configurations.
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The stacking of Ti3C2 with transition metal dihalide (TMDs) materials is an effective strategy to improve the physical properties of a single material, and the tuning of the related properties of these TMDs/Ti3C2 heterostructures is also an important scientific problem. In this work, we systematically investigated the effects of an external field and novel functional groups (S, Se, Cl, Br) on the structural and electronic properties of TMDs/Ti3C2X2 heterostructures. The results revealed that the lattice parameters and interlayer distance of TMDs/Ti3C2 increased with the addition of functional groups. Both tensile and compressive strain obviously increased the interlayer distance of MoS2/Ti3C2X2 (X = S, Se, Cl, Br) and MoSe2/Ti3C2X2 (X = Se, Br). In contrast, the interlayer distance of MoSe2/Ti3C2X2 (X = S, Cl) decreased with increasing compressive strain. Furthermore, the conductivity of TMDs/Ti3C2 increased due to the addition of functional groups (Cl, Br). Strain caused the bandgap of TMDs to narrow, and effectively adjusted the electronic properties of TMDs/Ti3C2X2. At 9% compressive strain, the conductivity of MoSe2/Ti3C2Cl2 increased significantly. Meanwhile, for TMDs/Ti3C2X2, the conduction band edge (CBE) and valence band edge (VBE) at the M and K points changed linearly under an electric field. This study provides valuable insight into the combined effects of an external field and novel functional groups on the related properties of TMDs/Ti3C2X2.
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Background: As a commonly used biomarker in rectal cancer (RC), the prognostic value of carcinoembryonic antigen (CEA) remains underexplored. This study aims to evaluate the prognostic value of pretreatment CEA/tumor volume in RC. Methods: This retrospective study included patients who underwent pretreatment magnetic resonance imaging (MRI) with histologically confirmed primary rectal adenocarcinoma from November 2012 to April 2018. Patients were divided into high-risk and low-risk groups according to the median values of CEA/Diapath (CEA to pathological diameter), CEA/DiaMRI (CEA to MRI tumor diameter), and CEA/VolMRI (CEA to MRI tumor volume). Cox regression analysis was utilized to determine the prognostic value of CEA, CEA/Diapath, CEA/DiaMRI, and CEA/VolMRI. Stepwise regression was used to establish nomograms for predicting disease-free survival (DFS) and overall survival (OS). Predictive performance was estimated by using the concordance index (C-index) and area under curve receiver operating characteristic (AUC). Results: A total of 343 patients [median age 58.99 years, 206 (60.06%) males] were included. After adjusting for patient-related and tumor-related factors, CEA/VolMRI was superior to CEA, CEA/Diapath, and CEA/DiaMRI in distinguishing high-risk from low-risk patients in terms of DFS [hazard ratio (HR) =1.83; P=0.010] and OS (HR =1.67; P=0.048). Subanalysis revealed that CEA/VolMRI stratified high death risk in CEA-negative individuals (HR =2.50; P=0.038), and also stratified low recurrence risk in CEA-positive individuals (HR =2.06; P=0.024). In the subanalysis of stage II or III cases, the highest HRs and the smallest P values were observed in distinguishing high-risk from low-risk patients according to CEA/VolMRI in terms of DFS (HR =2.44; P=0.046 or HR =2.41; P=0.001) and OS (HR =1.96; P=0.130 or HR =2.22; P=0.008). The nomograms incorporating CEA/VolMRI showed good performance, with a C-index of 0.72 [95% confidence interval (CI): 0.68-0.79] for DFS and 0.73 (95% CI: 0.68-0.80) for OS. Conclusions: Higher CEA/VolMRI was associated with worse DFS and OS. CEA/VolMRI was superior to CEA, CEA/Diapath, and CEA/DiaMRI in predicting DFS and OS. Pretreatment CEA/VolMRI may facilitate risk stratification and treatment decision-making.
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One of the main challenges in applying the immune checkpoint blockade to treat colorectal cancer (CRC) is the immunosuppressive tumor microenvironment. Owing to its excellent cancer cell killing ability and immune activation, mild photothermal therapy (PTT) has shown bright promise to sensitize tumors to immune checkpoint inhibition through turning the immunologically "cold" tumors into "hot" ones. Herein, a mild photothermal effect-assisted theragnostic nanodrug (MnO2@MPDA-PEG NPs) is developed by incorporating MnO2 into PEGylated-mesoporous polydopamine nanoparticles (MPDA-PEG NPs). The presence of PEG endows the theragnostic nanodrug with high biostability. After accumulation in colorectal tumor, the theragnostic nanodrug responds to the tumor microenvironment, leading to the simultaneous release of Mn2+ which serves as a magnetic resonance imaging (MRI) contrast agent for tumor imaging. The released Mn2+ could also promote mild photothermal treatment-induced immune response, including the maturation of BMDC cells. In vivo antitumor studies on a CT26 model demonstrate that MnO2@MPDA-PEG NPs could be a promising dual-imaging theragnostic nanodrug to potentiate the systemic antitumor immunities.
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Neoplasias Colorrectales , Nanopartículas , Línea Celular Tumoral , Neoplasias Colorrectales/terapia , Medios de Contraste , Humanos , Inmunoterapia , Indoles , Compuestos de Manganeso , Óxidos , Fototerapia/métodos , Polímeros , Microambiente TumoralRESUMEN
This paper presents a new method for combined measurements of persistent luminescence (PersL), thermoluminescence (TL), and mechanoluminescence (ML) of luminescent materials in the micrometer scale. Both the hardware and software designs have been illustrated in detail, and the experimental procedures to execute the emission map, PersL, TL, and ML measurements have been demonstrated. The PersL, TL, and ML properties of the SrAl2O4:Eu2+, Dy3+ micropowder, as well as the corresponding temperature variable emission spectra, have been measured. The results show good agreement with published investigations, indicating the accomplishment of designed functions. The instrument would be a powerful tool for exploring phosphorescent materials in the micrometer and smaller scales.
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Temperature-dependent and threshold behavior of Sm3+ ions on fluorescence properties of lithium niobate (LiNbO3, LN) single crystals were systematically investigated. The test materials, congruent LiNbO3 single crystals (Sm:LN), with various concentrations of doped Sm3+ ions from 0.2 to 2.0 mol.%, were grown using the Czochralski technique. Absorption spectra were obtained at room temperature, and photoluminescence spectra were measured at various temperatures in the range from 73 K to 423 K. Juddâ»Ofelt theory was applied to calculate the intensity parameters Ωt (t = 2, 4, 6) for 1.0 mol.% Sm3+-doped LiNbO3, as well as the radiative transition rate, Ar, branching ratio, ß, and radiative lifetime, τr, of the fluorescent 4G5/2 level. Under 409 nm laser excitation, the photoluminescence spectra of the visible fluorescence of Sm3+ mainly contains 568, 610, and 651 nm emission spectra, corresponding to the energy level transitions of 4G5/2â6H5/2, 4G5/2â6H7/2, and 4G5/2â6H9/2, respectively. The concentration of Sm3+ ions has great impact on the fluorescence intensity. The luminescence intensity of Sm (1.0 mol.%):LN is about ten times as against Sm (0.2 mol.%):LN at 610 nm. The intensity of the fluorescence spectra were found to be highly depend on temperature, as well as the concentration of Sm3+ ions in LiNbO3 single crystals, as predicted; however, the lifetime changed little with the temperature, indicating that the temperature has little effect on it, in Sm:LN single crystals. Sm:LN single crystals, with orange-red emission spectra, can be used as the active material in new light sources, fluorescent display devices, UV-sensors, and visible lasers.