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At least 73 records · Page 4

Spatial-Spectral Representation for X-Ray Fluorescence Image Super-Resolution

X-ray fluorescence (XRF) scanning of works of art is becoming an increasing popular nondestructive analyticalmethod. The high quality XRF spectra is necessary to obtain significant information on both major and minor elements used for characterization and provenance analysis. However, there is a tradeoff between the spatial resolution of an XRF scan and the signalto- noise ratio (SNR) of each pixel’s spectrum, due to the limited scanning time. In this project, we propose an XRF image super-resolution method to address this tradeoff; thus, obtaining a high spatial resolution XRF scan with high SNR. We fuse a lowresolution XRF image and a conventional RGB high-resolution image into a product of both high spatial and high spectral resolution XRF image. There is no guarantee of a one to one mapping between XRF spectrum and RGB color since, for instance, paintings with hidden layers cannot be detected in visible but can in X-ray wavelengths. We separate the XRF image into the visible and nonvisible components. The spatial resolution of the visible component is increased utilizing the high-resolution RGB image, whereas the spatial resolution of the non-visible component is increased using a total variation super-resolution method. Finally, the visible and nonvisible components are combined to obtain the final result.

Dai, Qiqin↗

NPQ (T) : a chlorophyll fluorescence parameter for rapid estimation and imaging of non-photochemical quenching of excitons in photosystem-II-associated antenna complexes: New, rapid probe of non-photochemical quenching

In photosynthesis, light energy is absorbed by light-harvesting complexes and used to drive photochemistry. However, a fraction of absorbed light is lost to non-photochemical quenching (NPQ) that reflects several important photosynthetic processes to dissipate excess energy. Currently, estimates of NPQ and its individual components (q E , q I , q Z and q T ) are measured from pulse-amplitude-modulation (PAM) measurements of chlorophyll fluorescence yield and require measurements of the maximal yield of fluorescence in fully dark-adapted material (F m ), when NPQ is assumed to be negligible. Unfortunately, this approach requires extensive dark acclimation, often precluding widespread or high-throughput use, particularly under field conditions or in imaging applications, while introducing artefacts when F m is measured in the presence of residual photodamaged centres. To address these limitations, we derived and characterized a new set of parameters, NPQ (T) , and its components that can be (1) measured in a few seconds, allowing for high-throughput and field applications; (2) does not require full relaxation of quenching processes and thus can be applied to photoinhibited materials; (3) can distinguish between NPQ and chloroplast movements; and (4) can be used to image NPQ in plants with large leaf movements. Finally, we discuss the applications benefits and caveats of both approaches.

chlorophyll fluorescence↗

Hyperspectral image reconstruction for x-ray fluorescence tomography

A penalized maximum-likelihood estimation is proposed to perform hyperspectral (spatio-spectral) image reconstruction for X-ray fluorescence tomography. The approach minimizes a Poisson-based negative log-likelihood of the observed photon counts, and uses a penalty term that has the effect of encouraging local continuity of model parameter estimates in both spatial and spectral dimensions simultaneously. The performance of the reconstruction method is demonstrated with experimental data acquired from a seed of arabidopsis thaliana collected at the 13-ID-E microprobe beamline at the Advanced Photon Source. The resulting element distribution estimates with the proposed approach show significantly better reconstruction quality than the conventional analytical inversion approaches, and allows for a high data compression factor which can reduce data acquisition times remarkably. In particular, this technique provides the capability to tomographically reconstruct full energy dispersive spectra without compromising reconstruction artifacts that impact the interpretation of results.

Fluorescence microscopy↗

Highly Efficient Blue OLEDs Based on Metal‐Assisted Delayed Fluorescence Pd(II) Complexes

Abstract A series of metal‐assisted delayed fluorescence (MADF) palladium(II) complexes, PdN1N, PdN1N‐dm, and PdN6N, are studied. Their 77 K photoluminescence emission spectra show a narrow primary emission peak at 464, 466, and 470 nm, respectively, with small vibronic peaks characteristic of many phosphorescent emitters. At room temperature (300 K), the dominant emission peaks for PdN1N, PdN1N‐dm, and PdN6N are slightly redshifted to 472, 470, and 476 nm, respectively. In the meantime, a broad sideband is also shown between 410 and 450 nm due to the MADF process. A blue device employing PdN1N‐dm demonstrates an electroluminescence emission peak at 476 nm and the maximum external quantum efficiency (EQE) of 25.1%. The high maximum EQE of the blue organic light‐emitting diode (OLED) device indicates that both the phosphorescence and the delayed fluorescence are very efficient. In addition, a stable OLED device of PdN1N‐dm gives a maximum EQE of 9.8% and the estimated operational lifetime LT 70 of 350 h at the practical luminance of 100 cd m −2 .

Zhu, Zhi‐Qiang↗

Spatially resolved density and ionization measurements of shocked foams using x-ray fluorescence

We present experiments at the Trident laser facility demonstrating the use of x-ray fluorescence (XRF) to simultaneously measure density, ionization state populations, and electron temperature in shocked foams. An imaging x-ray spectrometer obtained spatially resolved measurements of Ti K-α emission. Density profiles were measured from K-α intensity. Ti ionization state distributions and electron temperatures were inferred by fitting K-α spectra to spectra from CRETIN simulations. This work shows that XRF provides a powerful tool to complement other diagnostics to make equation of state measurements of shocked materials containing a suitable tracer element.

36 MATERIALS SCIENCE↗

X-ray nanoprobes and diffraction-limited storage rings: opportunities and challenges of fluorescence tomography of biological specimens

X-ray nanoprobes require coherent illumination to achieve optic-limited resolution, and so will benefit directly from diffraction-limited storage rings. Here, the example of high-resolution X-ray fluorescence tomography is focused on as one of the most voracious demanders of coherent photons, since the detected signal is only a small fraction of the incident flux. Alternative schemes are considered for beam delivery, sample scanning and detectors. One must consider as well the steps before and after the X-ray experiment: sample preparation and examination conditions, and analysis complexity due to minimum dose requirements and self-absorption. By understanding the requirements and opportunities for nanoscale fluorescence tomography, one gains insight into the R&D challenges in optics and instrumentation needed to fully exploit the source advances that diffraction-limited storage rings offer.

de Jonge, Martin D.↗

System and method for controlling depth of imaging in tissues using fluorescence microscopy under ultraviolet excitation following staining with fluorescing agents

A method is disclosed for analyzing a thin tissue sample and adapted to be supported on a slide. The tissue sample may be placed on a slide and exposed to one or more different exogenous fluorophores excitable in a range of about 300 nm-200 nm, and having a useful emission band from about 350 nm-900 nm, and including one or more fluorescent dyes or fluorescently labeled molecular probes that accumulate in tissue or cellular components. The fluorophores may be excited with a first wavelength of UV light between about 200 nm-290 nm. An optical system collects emissions from the fluorophores at a second wavelength, different from the first wavelength, which are generated in response to the first wavelength of UV light, to produce an image for analysis.

47 OTHER INSTRUMENTATION↗

Self-assembly of [UO{sub 2}X{sub 4}]{sup 2−} (X=Cl, Br) dianions with γ substituted pyridinium cations: Structural systematics and fluorescence properties

Room temperature self-assembly of [UO{sub 2}X{sub 4}]{sup 2−} (X=Cl, Br) with γ substituted pyridinium cations has resulted in the formation of twelve compounds that were studied via single crystal X-ray diffraction and fluorescence spectroscopy. Systematic variation of electron donating groups on the pyridinium species is shown to influence the presence and/or strength of various supramolecular synthons, including hydrogen bonding and pi interactions. Combinations of such non-covalent interactions (NCIs) have given rise to a range of supramolecular assemblies, and are shown to influence uranyl emission by way of second sphere coordination to equatorial ligands. - Graphical abstract: Supramolecular assembly of the [UO{sub 2}Cl{sub 4}]{sup 2−} dianion with pyridinium cations is a viable synthetic route to the growth of uranyl containing single crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermally Activated Delayed Fluorescence (TADF) Path toward Efficient Electroluminescence in Purely Organic Materials: Molecular Level Insight

Since the seminal work of Tang and Vanslyke in 1987 on small-molecule emitters and that of Friend and co-workers in 1990 on conjugated-polymer emitters, organic light-emitting diodes (OLEDs) have attracted much attention from academia as well as industry, as the OLED market is estimated to reach the $30B mark by the end of 2018. In these first-generation organic emitters, on the basis of simple spin statistics, electrical excitation resulted in the formation of ~25% singlet excitons and ~75% triplet excitons. Radiative decay of the singlet excitons to the singlet ground state leads to a prompt fluorescence emission, while the triplet excitons only lead to weak phosphorescence due to the very small spin-orbit couplings present in purely organic molecules. The consequence is a ca. 75% energy loss, which triggered wide-ranging efforts to try and harvest as many of the triplet excitons as possible. In 1998, Thompson, Forrest, and their co-workers reported second-generation OLED emitters based on coordination complexes with heavy transition metals (e.g., iridium or platinum). Here, the triplet excitons stimulate efficient and fast phosphorescence due to the strong spin-orbit couplings enabled by the heavy-metal atoms. Internal quantum efficiencies (IQE) up to 100% have been reported, which means that for every electron injected into the device, a photon is emitted. Here, while these second-generation emitters are those mainly exploited in current OLED applications, there is strong impetus from both cost and environmental standpoints to find new ways of exploiting purely organic emitters, which in addition can offer greater flexibility to fine tune the electronic and optical properties by exploiting the synthetic organic chemistry toolbox.

36 MATERIALS SCIENCE↗

Intramolecular Noncovalent Interactions Facilitate Thermally Activated Delayed Fluorescence (TADF)

In the conventional molecular design of thermally activated delayed fluorescence (TADF) organic emitters, simultaneously achieving a fast rate of reverse intersystem crossing (RISC) from the triplet to the singlet manifold and a fast rate of radiative decay is a challenging task. A number of recent experimental data, however, point to TADF emitters with intramolecular π-π interactions as a potential pathway to overcome the issue. Here, we report a comprehensive investigation of TADF emitters with intramolecular π…π or lone-pair…π non-covalent interactions. We uncover the impact of those intramolecular non-covalent interactions on the TADF properties. In particular, we find that folded geometries in TADF molecules can trigger lone-pair…π interactions, introduce a n → π* character of the relevant transitions, enhance the singlet-triplet spin-orbit coupling, and ultimately greatly facilitate the RISC process. Furthermore, this work provides a robust foundation for the molecular design of a novel class of highly efficient TADF emitters in which intramolecular non-covalent interactions play a critical function.

36 MATERIALS SCIENCE↗