Filtern
Dokumenttyp
- Zeitschriftenartikel (12)
- Corrigendum (1)
Sprache
- Englisch (13)
Schlagworte
- Lanthanide (4)
- Nano (3)
- Sensor (3)
- Temperature (3)
- Upconversion (3)
- Fluorescence (2)
- Monitoring (2)
- Particle (2)
- Quality assurance (2)
- Transmission function (2)
Organisationseinheit der BAM
- 1 Analytische Chemie; Referenzmaterialien (6)
- 1.2 Biophotonik (6)
- 6 Materialchemie (3)
- 6.1 Oberflächen- und Dünnschichtanalyse (3)
- 4 Material und Umwelt (2)
- 4.0 Abteilungsleitung und andere (1)
- 4.1 Biologische Materialschädigung und Referenzorganismen (1)
- 5 Werkstofftechnik (1)
- 5.1 Mikrostruktur Design und Degradation (1)
We report the results of a Versailles Project on Advanced Materials and Standards interlaboratory study on the intensity scale calibration of x-ray photoelectron spectrometers using low-density polyethylene (LDPE) as an alternative material to gold, silver, and copper. An improved set of LDPE reference spectra, corrected for different instrument geometries using a quartz-monochromated Al Kα x-ray source, was developed using data provided by participants in this study. Using
these new reference spectra, a transmission function was calculated for each dataset that participants provided. When compared to a similar calibration procedure using the NPL reference spectra for gold, the LDPE intensity calibration method achieves an absolute offset of ∼3.0% and a systematic deviation of ±6.5% on average across all participants. For spectra recorded at high pass energies (≥90 eV), values of absolute offset and systematic deviation are ∼5.8% and ±5.7%, respectively, whereas for spectra collected at lower pass energies (<90 eV), values of absolute offset and systematic deviation are ∼4.9% and ±8.8%, respectively; low pass energy spectra perform worse than the global average, in terms of systematic deviations, due to diminished count rates and signal-to-noise ratio. Differences in absolute offset are attributed to the surface roughness of the LDPE induced by sample preparation. We further assess the usability of LDPE as a secondary reference material and comment on its performance in the presence of issues such as variable dark noise, x-ray warm up times, inaccuracy at low count rates, and underlying spectrometer problems. In response to participant feedback and the results of the study, we provide an updated LDPE intensity calibration protocol to address the issues highlighted in the interlaboratory study. We also comment on the lack of implementation of a consistent and traceable intensity calibration method across the community of x-ray photoelectron spectroscopy (XPS) users and, therefore, propose a route to achieving this with the assistance of instrument manufacturers, metrology laboratories, and experts leading to an international standard for XPS intensity scale calibration.
The lead authors failed to name two collaborators as co-authors. The authors listed should include:
Miss Claudia L. Compean-Gonzalez (ORCID:
0000-0002-2367-8450) and Dr. Giacomo Ceccone (ORCID:
0000-0003-4637-0771).
These co-authors participated in VAMAS project A27, provided data that were analyzed and presented in this publication (and supporting information), and reviewed the manuscript before submission.
NaYF4:Yb3+/Tm3+@NaGdF4:Nd3+/Yb3+ upconversion nanoparticles (UCNPs) were prepared using a solvothermal method, and the effects of key factors such as the content of sensitiser Nd 3+ and Yb3+ on their luminescence properties were investigated. The nanoparticles are homogeneous in size and well dispersed. Under 808 nm excitation, it can produce strong upconversion fluorescence. At the same time, the nanoparticles have good temperature-sensing properties at the thermally coupled energy levels of 700 nm and 646 nm for Tm3+. Using its fluorescence intensity ratio (FIR), accurate temperature measurements can be performed, and it has been found that it exhibits different temperature sensing properties in low and high-temperature regions. The maximum relative sensitivity was found to be 0.88% K-1 and 1.89% K-1 for the lowtemperature region of 285 K-345 K and the high-temperature region of 345 K-495 K. The nanoparticles were applied to the internal temperature measurement of lithium batteries and the actual high-temperature environment, respectively, and were found to have good temperature measurementt performance.
The core−shell NaYF4:Yb3+/Tm3+@NaYF4:Yb3+ upconversion nanoparticles were successfully prepared by a solvothermal method, and a layer of mesoporous silica (mSiO2) was successfully coated on the periphery of the core−shell nanoparticles to transform their surface from lipophilic to hydrophilic, further expanding their applications in biological tissues. The physical phase, morphology, structure, and fluorescence properties were characterized by X-ray diffraction (XRD), field emission transmission electron microscopy (TEM), Fourier infrared spectroscopy (FT-IR), ζ potential analysis, and fluorescence spectroscopy. It was found that the material has a hexagonal structure with good hydrophilicity and emits intense fluorescence under 980 nm pump laser excitation. The non-contact temperature sensing performance of nanoparticles was evaluated by analyzing the upconversion fluorescence of Tm3+ (1G4 → 3F4 and 3F3 → 3H6) in the temperature range of 284−344 K. The absolute and relative sensitivities were found to be 0.0067 K−1 and 1.08 % K−1, respectively, with high-temperature measurement reliability and good temperature cycling performance. More importantly, its temperature measurement in phosphate-buffered saline (PBS) solution is accurate. In addition, the temperature of the cells can be increased by adjusting the laser power density and laser irradiation time. Therefore, an optical temperature sensing platform was built to realize the application of real-time monitoring of cancer cell temperature and the dual function of photothermal therapy.
The allergenic potential of airborne proteins may be enhanced via post-translational modification induced by air pollutants like ozone (O3) and nitrogen dioxide (NO2). The molecular mechanisms and kinetics of the chemical modifications that enhance the allergenicity of proteins, however, are still not fully understood. Here, protein tyrosine nitration and oligomerization upon simultaneous exposure of O3 and NO2 were studied in coated-wall flow-tube and bulk solution experiments under varying atmospherically relevant conditions (5–200 ppb O3, 5–200 ppb NO2, 45–96% RH), using bovine serum albumin as a model protein. Generally, more tyrosine residues were found to react via the nitration pathway than via the oligomerization pathway. Depending on reaction conditions, oligomer mass fractions and nitration degrees were in the ranges of 2.5–25% and 0.5–7%, respectively. The experimental results were well reproduced by the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). The extent of nitration and oligomerization strongly depends on relative humidity (RH) due to moisture-induced phase transition of proteins, highlighting the importance of cloud processing conditions for accelerated protein chemistry. Dimeric and nitrated species were major products in the liquid phase, while protein oligomerization was observed to a greater extent for the solid and semi-solid phase states of proteins. Our results show that the rate of both processes was sensitive towards ambient ozone concentration but rather insensitive towards different NO2 levels. An increase of tropospheric ozone concentrations in the Anthropocene may thus promote pro-allergic protein modifications and contribute to the observed increase of allergies over the past decades.
Evolution relies on the availability of genetic diversity for fitness-based selection. However, most deoxyribonucleic acid (DNA) viruses employ DNA polymerases (Pol) capable of exonucleolytic proofreading to limit mutation rates during DNA replication. The relative genetic stability produced by high-fidelity genome replication can make studying DNA virus adaptation and evolution an intensive endeavor, especially in slowly replicating viruses. Here, we present a proofreading-impaired Pol mutant (Y547S) of Marek’s disease virus that exhibits a hypermutator phenotype while maintaining unimpaired growth in vitro and wild-type (WT)-like pathogenicity in vivo. At the same time, mutation frequencies observed in Y547S virus populations are 2–5-fold higher compared to the parental WT virus. We find that Y547S adapts faster to growth in originally non-permissive cells, evades pressure conferred by antiviral inhibitors more efficiently, and is more easily attenuated by serial passage in cultured cells compared to WT. Our results suggest that hypermutator viruses can serve as a tool to accelerate evolutionary processes and help identify key genetic changes required for adaptation to novel host cells and resistance to antiviral therapy. Similarly, the rapid attenuation achieved through adaptation of hypermutators to growth in cell culture enables identification of genetic changes underlying attenuation and virulence, knowledge that could practically exploited, e.g. in the rational design of vaccines.
NaYF4 as the core and NaGdF4 as the outer layer were used to obtain
NaYF4:Yb3+/Tm3+@NaYF4:Ce3+/Eu3+ nanoparticles. Physical and morphological investigations indicated that the obtained nanoparticles were prepared in a hexagonal shape, with the NaGdF4 shell layer uniformly encapsulated on the NaYF4 core.
Strong Tm3+ upconversion emission peaks were observed for a 980-nm-laser-excited sample, while strong Eu3+ downconversion emission peaks were observed for a 254-nm-laser-excited sample. By zonal doping of Tm3+ and Eu3+, their fluorescence intensity can be significantly increased; more importantly, simultaneous temperature measurements with dual-mode upconversion/downconversion can be achieved. The temperature measurement properties of the dual mode were also investigated, and it was discovered that the upconversion 3F3 → 3H6 and 1G4 → 3F4 thermocouple energy levels gave the best temperature measurements with maximum absolute and relative sensitivities of 0.0877 K−1 and 1.95% K−1, respectively, which are better than the current temperature measurement sensitivities of most rare-earth-based materials. This material was prepared as fiber-optic temperature-sensing probes to detect the temperature in the environment in real time and was found to perform excellently for temperature measurement.
The NaYF4: Yb3+/Tm3+@NaYF4@β-CD upconversion nanoparticles were successfully prepared by the solvothermal method, and the samples were pure hexagonal phase with good crystallinity and homogeneous size, asevidenced by XRD and TEM analysis. The FT-IR analysis shows that β-CD is successfully encapsulated on the surface of NaYF4: Yb3+/Tm3+@NaYF4 nanoparticles. The fluorescence intensity 3and lifetime were significantly increased after coating the inert layer on the surface of core nanoparticles. After further surface modification of β-CD, the fluorescence intensity and fluorescence lifetime were reduced, but the overall fluorescence was stronger. Temperature measurements using the fluorescence intensity ratio technique were found to have relatively low reliability and absolute sensitivity for temperature measurements using thermally coupled energy levels. However, the reliability of temperature measurements using non-thermally coupled energy levels is significantly higher and the absolute sensitivity is much higher than for measurements at thermally coupled levels. Since the maximum absolute sensitivity, maximum relative sensitivity and minimum temperature resolution are determined to be 0.1179 K-1, 2.19 %K 1 and 0.00019 K, respectively, NaYF4: Yb3+/Tm3+@NaYF4@β-CD upconversion nanoparticles are expected to be widely used in the biomedical field due to their feasibility, reliability, non-toxicity and harmlessness.
Hierarchical microstructures are created when additional γ particles form in γ’ precipitates and they are linked to improved strength and creep properties in high-temperature alloys. Here, we follow the formation and evolution of a hierarchical microstructure in Ni86.1Al8.5Ti5.4 by in situ synchrotron X-ray diffraction at 1023 K up to 48 h to derive the lattice parameters of the γ matrix, γ’ precipitates and γ particles and misfits between phases. Finite element method-based computer simulations of hierarchical microstructures allow obtaining each phase's lattice parameter, thereby aiding peak identification in the in situ X-ray diffraction data. The simulations further give insight into the heterogeneous strain distribution between γ’ precipitates and γ particles, which gives rise to an anisotropic diffusion potential that drives the directional growth of γ particles. We rationalize a schematic model for the growth of γ particles, based on the Gibbs-Thomson effect of capillary and strain-induced anisotropic diffusion potentials. Our results highlight the importance of elastic properties, elastic anisotropy, lattice parameters, and diffusion potentials in controlling the behavior and stability of hierarchical microstructures.
A series of NaYF4:Yb3+/Tm3+@NaYF4:Yb3+/Er3+ nanoparticles doped with Tm3+ and Er3+ were successfully prepared by the solvothermal method. Under 980 nm laser excitation, intense upconversion emission peaks of Tm3+ and Er3+ were observed for all samples. By doping Tm3+ and Er3+ with core–shell partitioning, not only a significant increase in fluorescence intensity could be achieved, but also simultaneous temperature measurements on multiple thermocouple energy levels could be realised. In addition, the temperature sensing performance of different thermocouple energy levels was also investigated, and it was found that the 3 F3 → 3 H6 and 1 G4 → 3 F4 thermocouple energy level pairs of Tm3+ were the best, with maximum absolute sensitivity and maximum relative sensitivity of up to 0.0250 K−1 and 2.155% K−1 respectively, higher than the sensitivity of other thermocouple energy levels. It has a temperature resolution of less than 0.0139 K, which is lower than that of most materials available today. By using this material as a probe to build a fiber optic temperature sensor platform, it was found to have reliable temperature measurement performance.