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Fluorescein-sensitized Au/g-C3N4 nanocomposite for enhanced photocatalytic hydrogen evolution under visible light
Highlights: • Preparation of Au/g-C{sub 3}N{sub 4} composite through protonation, adsorption and reduction. • Au nanoparticles with average diameter of 4.1 nm are homogeneous deposited on g-C{sub 3}N{sub 4}. • The H{sub 2} evolution rate of Au/g-C{sub 3}N{sub 4} raises by 22 times after fluorescein sensitization. • Efficient transfer of photo-generated electrons among fluorescein, g-C{sub 3}N{sub 4} and Au. - Abstract: Au/g-C{sub 3}N{sub 4} composite is prepared through protonation of g-C{sub 3}N{sub 4}, followed by electrostatic adsorption of AuCl{sub 4{sup {sub −}}} and subsequent chemical reduction. The homogeneous deposition of Au nanoparticles with an average diameter of 4.1 nm on g-C{sub 3}N{sub 4} is confirmed by TEM measurement. Compared with pure g-C{sub 3}N{sub 4}, Au/g-C{sub 3}N{sub 4} composite exhibits a significant improvement in the photocatalytic activity for H{sub 2} production from water in the presence of triethanolamine as sacrificial electron donor under visible light irradiation (λ > 420 nm). Significantly, the rate of H{sub 2} production increases more than 22 times by adding fluorescein in the photocatalytic reaction system. It is more than 25 times higher than that of protonated g-C{sub 3}N{sub 4} in the presence of fluorescein. Based on our experimental results, the mechanism of photocatalytic activity for H{sub 2} evolution over fluorescein-sensitized Au/g-C{sub 3}N{sub 4} nanocomposite is accordingly proposed. The highly-improved performance is ascribed to the efficient transfer of photo-generated electrons among photo-excited fluorescein molecule, g-C{sub 3}N{sub 4} and Au, which is supported by photoluminescence spectra and transient photocurrent responses.
Molecular engineering of fluorescein dyes as complementary absorbers in dye co-sensitized solar cells
Fluorescein dye derivatives exhibit extended optical absorption up to 500 nm, rendering these compounds suitable as co-absorbers in dye-sensitized solar cells (DSCs). A molecular engineering approach is presented, which embraces this intrinsic optical attribute of fluoresceins, while modifying the dye chemistry to enhance their light harvesting efficiency, in order to effectively tailor them for DSC applications. This approach first realizes relationships between the molecular structure and the optoelectronic properties for a series of five a priori known (parent) fluorescein dyes: 5-carboxyfluorescein (1), a mixture of m -carboxyfluorescein where m = 5 or 6 (2), 5-carboxyfluorescein diacetate (3), 6-carboxyfluorescein diacetate (4), a mixture of n -carboxy-2',7'-dichlorofluorescein diacetate where n = 5 or 6 (5). The first step in this approach combines, where available, experimental and computational methods so that electronic structure calculations can also be validated for representative fluorescein dyes. Such calculations can then be used reliably to predict the structure and properties of fluorescein dyes for cases where experimental data are lacking. Structure-function relationships established from this initial step inform the selection of parent dye 1 that is taken forward to the second step in molecular engineering: in silico chemical derivation to re-functionalize 1 for DSC applications. For this purpose, computational calculations are used to extend the charge conjugation in 1 between its donor and acceptor moieties. These structural modifications result in a bathochromic shift of the lowest excitation by ~1.3-1.9 eV (100-170 nm), making the dye optically absorb in the visible region. Further calculations on dye molecules adsorbed onto the surface of a TiO 2 cluster are used to investigate the dye sensitization behavior via dye adsorption energies and anchoring modes. The results of this theoretical investigation lead to two molecularly engineered fluoresceins being proposed to act as co-sensitizers together with a rhodamine dye. This combination of three dyes ensures chemical compatibility, panchromatic absorption, and restores optical absorption dipping otherwise observed in a DSC device at ~350-400 nm owing to the I-/I- 3 electrolyte. Altogether, the results of this study demonstrate that molecular engineering can be used to identify suitable chemical modifications for organic dyes with improved light harvesting properties for photovoltaic applications.
Integrity Assessment of Hanford 242-A Evaporator Facility E-A-1 Re-boiler Vessel via Fluorescein Liquid Tracer Test Methods - 17357
The 242-A Evaporator Facility is critical to the United States Department of Energy's (DOE) Hanford Site clean-up mission due to limited space within the existing Double-Shell Tanks (DSTs) used to store nuclear and chemical waste until future processing. The 242-A Evaporator Facility is currently the sole waste volume reduction process used at Hanford, and the E-A-1 Re-boiler is essential to the Evaporator process. Due to the potential for cross-contamination between the Re-boiler tubes through which waste passes and the tube sheets of uncontaminated steam, an assessment of the Re-boiler vessel's integrity is required for continuing operations of the facility. In order to meet these requirements, an independent integrity assessment was designed to use fluorescein liquid tracer (LT) to verify the leak-tightness of the Re-boiler vessel in accordance with Washington River Protection Solutions, LLC (WRPS) tightness test standards, as well as, the ASME Boiler and Pressure Vessel (B and PV) Code, Section III, Division 1, NB-6300. LT test methodologies were evaluated and determined to be appropriate for a vessel with restricted access, such as the E-A-1 Re-boiler, as it provided the needed sensitivity, reliability, and cost; as well as, exceeded the leak-tightness specifications required by both WRPS and ASME B and PV Code standards. The integrity test requires water laced with fluorescein be circulated through the waste processing loop of the 242-A Evaporator and samples of steam condensate be collected and analyzed for traces of fluorescein to determine leak-tightness. Liquid condensate sampling was conducted prior to and during testing and the samples were analyzed for fluorescein tracer to determine the amount of fluorescein that flowed out of the tubes of the Re-boiler into the steam side of the vessel. Given the established criteria for 'leak-tight,' test results determined that the Re-boiler passed the integrity assessment. After further scrutiny of the 2014 test and data results, it was determined that although the Re-boiler was 'leak-tight,' as established by the test criteria, there was concern of future leakage. The DOE and the DOE Office of River Protection (ORP) requested that WRPS repeat the integrity assessment in two and a half years to determine if the potential leak was growing, which could threaten continuing operations of the 242-A Evaporator. The 2017 test has been redesigned using lessons learned from the 2014 test and was modified to account for ergonomic and safety considerations, ease of repeatability, and accuracy of results. The liquid tracer methodology and test plan developed for the Re-boiler will continue to be implemented in 5 year increments to monitor current and future integrity. The method may also prove useful for other aging components across the Hanford Site, where appropriate. (authors)
Ultrafast Time-Resolved Studies on Fluorescein for Recognition Strands Architecture in Amyloid Fibrils
Protein aggregation is associated with numerous devastating diseases such as Alzheimer’s, Parkinson’s, and prion diseases. Development of therapeutics would benefit from knowledge of the structural organization of protein molecules in these amyloid aggregates, particularly in their aqueous biological milieu. However, detailed structural studies to date have been mainly on the solid state and have required large quantities of purified aggregate. Moreover, these conventional methods require the aggregated assembly to remain structurally stable over days or weeks required to perform the experiment, whereas the pathologically relevant species of in vivo aggregates may be shorter lived. Here, we show the organization of protein chains in dissolved amyloid aggregates can be readily determined spectroscopically using minute quantities of fluorescein-labeled protein segments in a matter of minutes. Specifically, we investigated the possibility of using the ultrafast dynamics of fluorescein to distinguish among three categories of β-sheet geometry: (1) antiparallel in-register, (2) parallel in-register, or (3) antiparallel out-of-register. Fluorescein, the most commonly used staining dye in biology and medicine, was covalently attached to the N-termini of peptide sequences selected from a library of known amyloid crystal structures. We investigated the aggregates in solution using steady-state and time-resolved absorption and fluorescence spectroscopy. We found that the dynamics of fluorescein relaxation from the excited state revealed amyloid structure-specific information. Particularly, the nonfluorescent cation form of fluorescein showed remarkable sensitivity to local environments created during aggregation. We demonstrate that time-resolved absorption is capable of differentiating strand organization in β-sheet aggregates when strong intermolecular coupling between chromophores occurs. Here, this approach can be useful in optical recognition of specific fibril architectures of amyloid aggregates.
Testing Fluorescence Lifetime Standards using Two-Photon Excitation and Time-Domain Instrumentation: Fluorescein, Quinine Sulfate and Green Fluorescent Protein
It is essential for everyone working with experimental science to be certain that their instruments produce reliable results, and for fluorescence lifetime experiments, information about fluorescence lifetime standards is crucial. A large part of the literature on lifetime standards dates back to the 1970s and 1980s, and the use of newer and faster measuring devices may deem these results unreliable. We have tested the three commonly used fluorophores fluorescein, quinine sulfate and green fluorescent protein for their suitability to serve as lifetime standards, especially to be used with two-photon excitation measurements in the time-domain. We measured absorption and emission spectra for the fluorophores to determine optimal wavelengths to use for excitation and detector settings. Fluorescence lifetimes were measured for different concentrations, ranging from 10{sup − 3} − 10{sup − 5} M, as well as for various solvents. Fluorescein was soluble in both ethanol, methanol and sulfuric acid, while quinine sulfate was only soluble in sulfuric acid. Green fluorescent protein was prepared in a commercial Tris-HCl, EDTA solution, and all three fluorophores produced stable lifetime results with low uncertainties. No siginificant variation with concentration was measured for any of the fluorophores, and all showed single-exponential decays. All lifetime measurements were carried out using two-photon excitation and lifetime data was obtained in the time-domain using time-correlated single-photon counting.
Selective and Sensitive Fluorescein-Benzothiazole Based Fluorescent Sensor for Zn{sup 2+} Ion in Aqueous Media
An efficient fluorescent sensor based on fluorescein-benzothiazole (FB) for Zn{sup 2+} ion was synthesized and characterized systematically. FB exhibited selective and sensitive recognition toward Zn{sup 2+} in MeCN-H{sub 2}O (v/v = 2/1) over other cations due to the spirolactam ring-opening power of Zn{sup 2+}. The complexation property of FB with Zn{sup 2+} ion was examined by {sup 1}H NMR, {sup 13}C NMR and FTIR experiments. The stoichiometric ratio of the FB-Zn{sup 2+} complex was determined from a Job plot to be 1:1. The binding constant (K{sub a}) of Zn{sup 2+} binding to FB was found to be 4.22 × 10{sup 4} M{sup − 1}, with a detection limit of 5.64 μM. In addition, the practical utility of FB was explored in the form of test strips. .
Phase conjugation by degenerate four wave mixing in disodium fluorescein solution in methanol
Organic dyes are known to show the resonant type of nonlinear optical properties, including phase conjugation. In the present work, disodium fluorescein in methanol is used as an organic nonlinear medium for degenerate four wave mixing at 532 nm to see the intensity dependence of the phase conjugate signal at different concentrations of the solution. It is observed that the maximum reflectivity of the signal occurs in a concentration range of 5 x 10(exp -3)/cu cm to 1.2 x 10(exp -2) g/cu cm. It is also observed that the intensity of the signal drops suddenly to less than half of its maximum outside the concentration range mentioned above. An investigation of the phase conjugate signal intensity by changing the delay time between probe signal and the forward pump is also examined. Briefly discussed is the possibility of population grating in dye liquids as a source of enhancing the third order susceptibility besides the other techniques mentioned in reference. The experiment is done by beam splitting the second harmonic (532 nm) of Nd:YAG laser, Q-switched at 20 pulses/sec (pulse width is approximately 8 and 200 mJ per pulse).
Human Tear-Film Evaporation Rates from Infrared Ocular-Surface Cooling and Fluorescein Breakup
Tear-film evaporation is critical for maintaining anterior-eye health and comfortable contact-lens wear. For the first time, we devise a quantitative method for ascertaining in-vivo tear evaporation rates (TERs) from simultaneous measurement of transient corneal surface cooling and fluorescein breakup.
Fluorescein and naphthol substrates for phosphatase assays
Fluorscein and naphthol substrates for phosphatase activity in soils detected by fluorometric assays - enzyme activity in soils by fluorescent emission
The solubility and other physicochemical properties of human gamma-globulin labeled with fluorescein isothiocyanate.
Solubility characteristics and electrophoretic and ultracentrifugal properties of human gamma globulins
MO-AB-BRA-04: Radiation Measurements with a DNA Double-Strand-Break Dosimeter
Purpose: Many types of dosimeters are used to measure radiation, but none of them directly measures the biological effect of this dose. The purpose here is to create a dosimeter that can measure the probability of double-strand breaks (DSB) for DNA, which is directly related to the biological effect of radiation. Methods: The dosimeter has DNA strands, which are labeled on one end with biotin and on the other with fluorescein. The biotin attaches these strands to magnetic beads. We suspended the DNA dosimeter in phosphate-buffered saline (PBS) as it matches the internal environment of the body. We placed small volumes (50µL) of the DNA dosimeter into tubes and irradiated these samples in a water-equivalent plastic phantom with several doses (three samples per dose). After irradiating the samples, a magnet was placed against the tubes. The fluorescein attached to broken DNA strands was extracted (called the supernatant) and placed into a different tube. The fluorescein on the unbroken strands remained attached to the beads in the tube and was re-suspended with 50µL of PBS. A fluorescence reader was used to measure the fluorescence for both the re-suspended beads and supernatant. To prove that we are measuring DSB, we tested dosimeter response with two different lengths of attached DNA strands (1 and 4 kilo-base pair). Results: The probability of DSB at the dose levels of 5, 10, 25, and 50 Gy were 0.05, 0.08, 0.12, and 0.19, respectively, while the coefficients of variation were 0.14, 0.07, 0.02, and 0.01, respectively. The 4 kilo-base-pair dosimeter produced 5.3 times the response of the 1 kilo-base-pair dosimeter. Conclusion: The DNA dosimeter yields a measurable response to dose that scales with the DNA strand length. The goal now is to refine the dosimeter fabrication to reproducibly create a low coefficient of variation for the lower doses. This work was supported in part by Yarmouk University (Irbid, Jordan) and CPRIT (RP140105)
Use of an ocular wound chamber for the prevention of exposure keratopathy in a guinea pig model
Abstract Current therapies available to treat and heal ocular surface injuries and periocular burns are frequently inadequate, costly, and labor intensive. To address these limitations, we have employed a flexible, semitransparent ocular wound chamber (OWC) to provide protection as well as a watertight seal to allow for the constant delivery of therapeutics to the ocular surface and surrounding periocular tissue. This study demonstrates the safety and utilization of the OWC on uninjured eyes and in our exposure keratopathy model. For initial safety studies ( N = 3 per group), the eyelids remained intact and the eye uninjured. A blepharotomy ( N = 6 per group) was performed to remove the upper and lower eyelids surrounding the left (OS) eye to create our exposure keratopathy model. Right (OD) eyes served as uninjured controls in all studies. Following OWC placement, 0.5 mL HPMC gel or balanced saline solution (BSS) was injected into the chamber. Animals were monitored daily and fully assessed via white light, fluorescein, and OCT imaging at least through 72 hours post OWC placement. In studies that included a blepharotomy, skin samples were analyzed by multiplex cytokine analysis. Results of safety experiments revealed no significant differences between treatment groups in corneal thickness, fluorescein staining, OCT imaging, or histological eye or skin sections when compared to control eyes. In our exposure keratopathy model, OWC treated eyes showed significantly less fluorescein uptake and also were found to have significantly lower levels of cytokines IL‐13 and IL‐5 in skin samples. These results demonstrate for the first time that treatment using the OWC device is not only safe, but significantly protects against blepharotomy‐induced exposure keratopathy. As a whole, this study advances our overall efforts to develop a feasible solution to treat ocular surface injuries, infections, and periocular burns.
Retinal Image Quality Assessment for Spaceflight-Induced Vision Impairment Study
Long-term exposure to space microgravity poses significant risks for visual impairment. Evidence suggests such vision changes are linked to cephalad fluid shifts, prompting a need to directly quantify microgravity-induced retinal vascular changes. The quality of retinal images used for such vascular remodeling analysis, however, is dependent on imaging methodology. For our exploratory study, we hypothesized that retinal images captured using fluorescein imaging methodologies would be of higher quality in comparison to images captured without fluorescein. A semi-automated image quality assessment was developed using Vessel Generation Analysis (VESGEN) software and MATLAB® image analysis toolboxes. An analysis of ten images found that the fluorescein imaging modality provided a 36% increase in overall image quality (two-tailed p=0.089) in comparison to nonfluorescein imaging techniques.
EGS Collab Testbed 1: Second Set Tracer Test Results
The EGS Collab project is developing ~10-20 m-scale field sites where fracture stimulation and flow models can be validated against controlled, small-scale, in-situ experiments. The first multi-well experimental site was established at the 4850 level in the Homestake Mine in Lead, South Dakota, where hydraulic fractures were created at an injection well drilled sub-horizontal from the drift. This file contains the second set of tracer data (also include the data uploaded previously, https://gdr.openei.org/submissions/1128) for the EGS Collab testbed. The tracer tests were conducted during October 2018 - November 2019. Injected tracers include DNA, C-dots (fluorescein nano particles), fluorescein, rhodamine-b, sodium chloride, lithium bromide and cesium iodine. The tracers have been detected in three flowing wells located about 7.5 to 9 meters away from the injection interval. The tracer breakthrough curves from these locations have been adjusted to account for the residence time in the injection and production tubing. The details about the tracer test can be found in Background and Methods of Tracer Tests (Mattson et al. (2019,a,b)) (also included in this package). References Mattson, E.D., Neupane, G., Plummer, M.A., Hawkins, A., Zhang, Y. and the EGS Collab Team 2019a. Preliminary Collab fracture characterization results from flow and tracer testing efforts. In Proceedings 44th Workshop on Geothermal Reservoir Engineering, edited, Stanford University, Stanford, California. Mattson, E.D., Neupane, G., Hawkins, A., Burghardt, J., Ingraham, M., Plummer, M., and the EGS Collab Team, 2019b. Fracture tracer injection response to pressure perturbations at an injection well. GRC Transactions, Vol. 43, 2019. Neupane, Ghanashyam, Earl Mattson, Adam Hawkins, Mitchell Plummer, and Yuran Zhang. EGS Collab Testbed 1: Tracer data sets. No. 1128. DOE Geothermal Data Repository; Idaho National Laboratory, 2019.
Electron Mobility and Trapping in Ferrihydrite Nanoparticles
Iron is the most abundant transition metal in the Earth's crust, and naturally occurring iron oxide minerals play a commanding role in environmental redox reactions. Although iron oxide redox reactions are well studied, their precise mechanisms are not fully understood. Recent work has shown that these involve electron transfer pathways within the solid, suggesting that overall reaction rates could be dependent on electron mobility. Initial ultrafast spectroscopy studies of iron oxide nanoparticles sensitized by fluorescein derivatives supported a model for electron mobility based on polaronic hopping of electron charge carriers between iron sites, but the constitutive relationships between hopping mobilities and interfacial charge transfer processes has remained obscured. We developed a coarse-grained lattice Monte Carlo model to simulate the collective mobilities and lifetimes of these photoinjected electrons with respect to recombination with adsorbed dye molecules for the essential nanophase ferrihydrite, and tested predictions made by the simulations using pump-probe spectroscopy. We acquired optical transient absorption spectra as a function of particle size and under a variety of solution conditions, and used cryogenic transmission electron microscopy to determine the aggregation state of the nanoparticles. We observed biphasic electron recombination kinetics over timescales that spanned picoseconds to microseconds, the slower regime of which was fit with a stretched exponential decay function. The recombination rates were weakly affected by nanoparticle size and aggregation state, suspension pH, and the injection of multiple electrons per nanoparticle. We conclude that electron mobility indeed limits the rate of interfacial electron transfer in these systems with the slowest processes relating to escape from deep traps, the presence of which outweighs the influence of environmental factors such as pH-dependent surface charge.
Plexcitons: The Role of Oscillator Strengths and Spectral Widths in Determining Strong Coupling
Strong coupling interactions between plasmon and exciton-based excitations have been proposed to be useful in the design of optoelectronic systems. However, the role of various optical parameters dictating the plasmon-exciton (plexciton) interactions is less understood. Herein, we propose an inequality for achieving strong coupling between plasmons and excitons through appropriate variation of their oscillator strengths and spectral widths. These aspects are found to be consistent with experiments on two sets of free-standing plexcitonic systems obtained by (i) linking fluorescein isothiocyanate on Ag nanoparticles of varying sizes through silane coupling and (ii) electrostatic binding of cyanine dyes on polystyrenesulfonate-coated Au nanorods of varying aspect ratios. Being covalently linked on Ag nanoparticles, fluorescein isothiocyanate remains in monomeric state, and its high oscillator strength and narrow spectral width enable us to approach the strong coupling limit. In contrast, in the presence of polystyrenesulfonate, monomeric forms of cyanine dyes exist in equilibrium with their aggregates: Coupling is not observed for monomers and H-aggregates whose optical parameters are unfavorable. The large aggregation number, narrow spectral width, and extremely high oscillator strength of J-aggregates of cyanines permit effective delocalization of excitons along the linear assembly of chromophores, which in turn leads to efficient coupling with the plasmons. Further, the results obtained from experiments and theoretical models are jointly employed to describe the plexcitonic states, estimate the coupling strengths, and rationalize the dispersion curves. The experimental results and the theoretical analysis presented here portray a way forward to the rational design of plexcitonic systems attaining the strong coupling limits.