Nanoscale Cathodoluminescence Thermometry with a Lanthanide-Doped Heavy-Metal Oxide in Transmission Electron Microscopy.

When navigated by the available energy of a system, often provided in the form of heat, physical processes or chemical reactions fleet on a free-energy landscape, thus changing the structure. In in situ transmission electron microscopy (TEM), where material structures are measured and manipulated inside the microscope while being subjected to external stimuli such as electrical fields, laser irradiation, or mechanical stress, it is necessary to precisely determine the local temperature of the specimen to provide a comprehensive understanding of material behavior and to establish the relationship among energy, structure, and properties at the nanoscale. Here, we propose using cathodoluminescence (CL) spectroscopy in TEM for in situ measurement of the local temperature. Gadolinium oxide particles doped with emissive europium ions present an opportunity to utilize them as a temperature probe in CL measurements via a ratiometric approach. We show the thermometric performance of the probe and demonstrate a precision of ±5 K in the temperature range from 113 to 323 K with the spatial resolution limited by the size of the particles, which surpasses other methods for temperature determination. With the CL-based thermometry, we further demonstrate measuring local temperature under laser irradiation.

Excited-State Kinetics of an Air-Stable Cyclometalated Iron(II) Complex.

The complex class [Fe(N^N^C)(N^N^N)]+ with an Earth-abundant metal ion has been repeatedly suggested as a chromophore and potential photosensitizer on the basis of quantum chemical calculations. Synthesis and photophysical properties of the parent complex [Fe(pbpy)(tpy)]+ (Hpbpy=6-phenyl-2,2'-bipyridine and tpy=2,2':6',2''-terpyridine) of this new chromophore class are now reported. Ground-state characterization by X-ray diffraction, electrochemistry, spectroelectrochemistry, UV/Vis, and X-ray spectroscopy in combination with DFT calculations proves the high impact of the cyclometalating ligand on the electronic structure. The photophysical properties are significantly improved compared to the prototypical [Fe(tpy)2 ]2+ complex. In particular, the metal-to-ligand absorption extends into the near-IR and the 3 MLCT lifetime increases by 5.5, whereas the metal-centered excited triplet state is very short-lived.

Native Fluorescence and Time Resolved Fluorescence Spectroscopic Characterization of Normal and Malignant Oral Tissues Under UV Excitation--an In Vitro Study.

The present work aims to investigates the native fluorescence and time resolved fluorescence spectroscopic characterization of oral tissues under UV excitation. The fluorescence emission spectra of oral tissues at 280 nm excitation were obtained. From the spectra, it was observed that the alteration in the biochemical and morphological changes present in tissues. Subsequently, the Full width at Half Maximum (FWHM) of every individual spectra of 20 normal and 40 malignant subjects were calculated. The student's t-test analysis reveals that the data were statistically significant (p = 0.001). The fluorescence excitation spectra at 350 nm emission of malignant tissues confirms the alteration in protein fluorescence with respect to normal counterpart. To quantify the observed spectral differences, the two ratio variables R1 = I275/I310 and R2 = I310/I328 were introduced in the excitation spectra. Among them, the Linear Discriminant Analysis (LDA) of R1 reveals better classification with 86.4 % specificity and 82.5 % sensitivity. The fluorescence decay kinetics of oral tissues was obtained at 350 nm emission and it was found that the decay kinetics was triple exponential. Then the ROC analysis of fractional amplitudes and component lifetime reveals that the average lifetime shows 77 % sensitivity and 70 % specificity with the cut off value 4.85 ns. Briefly, the average lifetime exhibits better statistical significance when compared to fractional amplitudes and component lifetimes.

Fluorescence spectroscopic characterization of salivary metabolites of oral cancer patients.

A pilot study has been carried out using human saliva in differentiating the normal subjects from that of oral squamous cell carcinoma (OSCC) patients, using the autofluorescence spectroscopy at 405nm excitation. A markable difference in the spectral signatures between the saliva of normal subjects and that of oral cancer patients has been noticed. The possible reasons for the altered spectral signature may be due to the presence of endogenous porphyrin, NAD(P)H and FAD in the exfoliated cells from saliva. The elevated level of porphyrin in saliva of OSCC patients may be attributed to the disturbances in the amino acid degradation pathway and heme biosynthetic pathway, during the transformation of normal into malignant cells. The integrated area under the curve of fluorescence emission spectrum at 405nm excitation and also fluorescence excitation spectrum for 625nm emission were compared for the saliva of normal and oral cancer patients. The area under the curve for the emission spectrum provides 85.7% sensitivity and 93.3% specificity, where as the fluorescence excitation spectrum discriminates the same with 84.1% sensitivity and 93.2% specificity.