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At least 73 records · Page 4

Molecular-scale Insights into Cooperativity Switching of x TAB Adsorption on Gold Nanoparticles

Quantifying adsorption behaviors is crucial for various applications such as catalysis, separation, and sensing, yet it is generally challenging to access in solution. Here, we report a combined experimental and computational study of the adsorption behaviors of alkyl-trimethylammonium bromides (xTAB), a class of ligands important for colloidal nanoparticle stabilization and shape control, with various alkyl chain lengths x on Au nanoparticles. We use density functional theory (DFT) to calculate xTAB binding energies on Au{111} and Au{110} surfaces with standing-up and lying-down configurations, which provides insights into the adsorption affinity and cooperativity differences of xTAB on these two facets. We demonstrate the key role of van der Waals interactions in determining the xTAB adsorption behavior. These computational results predict and explain the experimental discovery of xTAB’s adsorption behavior switch from stronger affinity, negative cooperativity to weaker affinity, positive cooperativity when the concentration of xTAB increases in solution. We also show that in the standing-up configuration, bilayer adsorption may occur on both facets, which can lead to different differential binding energies and consequently adsorption crossover between the two facets when the ligand concentration increases. Our combined experimental and computational approaches demonstrate a paradigm for gaining molecular-scale insights into adsorbate–surface interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Light Induced Processes in CsPbBr 3 –Au Hybrid Nanocrystals: Electron Transfer and Expulsion of Au

Semiconductor–metal heterostructures such as CsPbBr 3 –Au are useful in photocatalysis. When Au nanoparticles are deposited on the CsPbBr 3 nanocrystal surface, they efficiently quench the photoluminescence of the semiconductor. This process has been studied by femtosecond transient absorption spectroscopy measurements, which indicate that electron transfer to the Au nanoparticles occurs from both hot and relaxed electrons in the conduction band of CsPbBr 3 . The electron transfer rate constant is much larger for the hot electrons compared to the relaxed electrons. Under steady state photoirradiation of CsPbBr 3 –Au heterostructure, the photogenerated electrons from the excited CsPbBr 3 nanocrystals continue to charge the Au nanoparticles. After sufficient irradiation, the gold nanoparticles dissociate from the CsPbBr 3 surface and aggregate into larger size gold nanoparticles. The expulsion of gold nanoparticles restores the original luminescence behavior of CsPbBr 3 nanocrystals. The spectroscopic and morphological studies provide insight into the expulsion of gold nanoparticles in photoirradiated CsPbBr 3 –Au heterostructures.

14 SOLAR ENERGY↗

Determining Concentration of Nanoparticles from Ellipsometry

A method of using ellipsometry or polarization analysis of light in total internal reflection of a surface to determine the number density of gold nanoparticles on a smooth substrate has been developed. The method can be modified to enable determination of densities of sparse distributions of nanoparticles in general, and is expected to be especially useful for measuring gold-nanoparticle-labeled biomolecules on microarrays. The method is based on theoretical calculations of the ellipsometric responses of gold nanoparticles. Elements of the calculations include the following: For simplicity, the gold nanoparticles are assumed to be spherical and to have the same radius. The distribution of gold nanoparticles is assumed to be a sub-monolayer (that is, sparser than a monolayer). The optical response of the sub-monolayer is modeled by use of a thin-island-film theory, according to which the polarizabilities parallel and perpendicular to the substrate are functions of the wavelength of light, the dielectric functions (permittivities expressed as complex functions of frequency or wavelength) of the gold and the suspending medium (in this case, the suspending medium is air), the fraction of the substrate area covered by the nanoparticles, and the radius of the nanoparticles. For the purpose of the thin-island-film theory, the dielectric function of the gold nanoparticles is modeled as the known dielectric function of bulk gold plus a correction term that is necessitated by the fact that the mean free path length for electrons in gold decreases with decreasing radius, in such a manner as to cause the imaginary part of the dielectric function to increase with decreasing radius (see figure). The correction term is a function of the nanoparticle radius, the wavelength of light, the mean free path and the Fermi speed of electrons in bulk gold, the plasma frequency of gold, and the speed of light in a vacuum. These models are used to calculate ellipsometric responses for various concentrations of gold nanoparticles having an assumed radius. The modeled data indicates distinct spectral features for both the real and the imaginary part of the dielectric function. An ellipsometric measurement would determine this distinct feature and thus can be used to measure nanoparticle concentration. By "ellipsometric responses" is meant the intensities of light measured in various polarization states as functions of the angle of incidence and the polarization states of the incident light. These calculated ellipsometric responses are used as calibration curves: Data from subsequent ellipsometric measurements on real specimens are compared with the calibration curves. The concentration of the nanoparticles on a specimen is assumed to be that of the calibration curve that most closely matches the data pertaining to that specimen.

Venkatasubbarao, Srivatsa↗

INBOUND APPOINTEE PUBLICATION Importance of Substrate-Particle Repulsion for Protein-Templated Assembly of Metal Nanoparticles

We study the protein-directed assembly of colloidal gold nanoparticles on de novo designed protein nanofiber templates. Using sequential assembly on glass substrates, we attach of positively-charged gold nanoparticles to protein nanofibers engineered to have a high density of negatively-charged surface residues. Using a combination of electron and optical microscopy, we measure the density of particle attachment and characterize binding specificity. By varying nanoparticle size and pH of the solution, we explore the importance of charge-dependent particle-fiber and particle-substrate interactions. We find an inverse correlation between particle size and attachment density to the protein nanofibers, attributed to the balance between size-dependent electrostatic particle-fiber attraction and particle-substrate repulsion. We show pH-dependent particle attachment density and binding specificity in relation to the protonation fraction of each assembly layer. Finally, we employ hyperspectral scattering microscopy to draw conclusions about particle density and interparticle spacings of optically-observable particle assemblies.

Guye, Kathryn N.↗

Characterization of a Pixelated Cadmium Telluride Detector System Using a Polychromatic X-Ray Source and Gold Nanoparticle-Loaded Phantoms for Benchtop X-Ray Fluorescence Imaging

In this paper, the imaging dose and scan time have been considered as the two major constraints for routine benchtop x-ray fluorescence computed tomography (XFCT) imaging. One way to address this issue is to acquire x-ray fluorescence (XRF) signals in parallel through a 2D array of single-crystal detectors or a pixelated detector along with the cone-beam x-ray source. To identify a detector system suitable for this purpose, a commercially available, fully spectroscopic cadmium telluride (CdTe) pixelated detector, HEXITEC (High-Energy X-ray Imaging Technology), was tested under the experimental conditions optimized for benchtop XFCT imaging of gold nanoparticles (GNPs). Specifically, two different parallel-hole stainless steel collimators were fabricated and coupled with the detector for seamless integration into our existing benchtop cone-beam XFCT system. After the detector deployment, this benchtop XFCT system was used to detect XRF photons from GNP-loaded phantoms. A pixel-merging algorithm was introduced to enhance the sensitivity of XRF photon detection thereby minimizing the scan time. The effect of pixel-level charge sharing correction algorithms was investigated within the context of benchtop XFCT imaging. The detector energy resolution, in terms of the full width at half maximum (FWHM) values at different gold K-shell XRF energies, was also determined. Of the two charge sharing correction algorithms examined, the charge sharing addition gave better sensitivity than the charge sharing discrimination (csd). On the other hand, under the current experimental conditions, the energy resolution of the HEXITEC detector was the best with the csd and estimated to be 1.56 keV FWHM at 66-69 keV photon energy. Overall, despite some degradation of the detector energy resolution (compared with typical single crystal CdTe detectors), the HEXITEC detector enabled parallel data acquisition under the experimental conditions typical of benchtop XFCT imaging and operated well within our benchtop XFCT setup.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Coherent Phonon Dynamics in Plasmonic Gold Tetrahedral Nanoparticle Ensembles

Coherent phonon modes supported by plasmonic nanoparticles offer prospective applications in chemical and biological sensing. Whereas characterization of these phonon modes often requires single particle measurements, synthetic routes to narrow size distributions of nanoparticles permit ensemble investigations. Recently, the synthesis of highly monodisperse gold tetrahedral nanoparticles with tunable edge length and corner sharpness has been developed. Herein, we characterize a size series of these nanoparticles in colloidal dispersion via transient absorption spectroscopy to examine their mechanical and plasmonic responses upon photoexcitation. Oscillations of transient absorption signals are observed in the plasmon resonance and correspond to the lowest order radial breathing modes of the nanoparticles, the frequencies of which are affected by edge length and truncation of the corners. Furthermore, quality factor values ranging from 10 to 15 are observed for the oscillations that convey potential utility in mass-sensing and plasmon-exciton coupling photonics schemes. Finite-difference time domain and finite element analysis calculations establish the specific optically-relevant phonon modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machine Learning Discrimination and Ultrasensitive Detection of Fentanyl Using Gold Nanoparticle-Decorated Carbon Nanotube-Based Field-Effect Transistor Sensors

The opioid overdose crisis is a global health challenge. Fentanyl, an exceedingly potent synthetic opioid, has emerged as a leading contributor to the surge in opioid-related overdose deaths. The surge in overdose fatalities, particularly due to illicitly manufactured fentanyl and its contamination of street drugs, emphasizes the urgency for drug-testing technologies that can quickly and accurately identify fentanyl from other drugs and quantify trace amounts of fentanyl. In this paper, gold nanoparticle (AuNP)-decorated single-walled carbon nanotube (SWCNT)-based field-effect transistors (FETs) are utilized for machine learning-assisted identification of fentanyl from codeine, hydrocodone, and morphine. The unique sensing performance of fentanyl led to use machine learning approaches for accurate identification of fentanyl. Employing linear discriminant analysis (LDA) with a leave-one-out cross-validation approach, a validation accuracy of 91.2% is achieved. Meanwhile, density functional theory (DFT) calculations reveal the factors that contributed to the enhanced sensitivity of the Au-SWCNT FET sensor toward fentanyl as well as the underlying sensing mechanism. Finally, fentanyl antibodies are introduced to the Au-SWCNT FET sensor as specific receptors, expanding the linear range of the sensor in the lower concentration range, and enabling ultrasensitive detection of fentanyl with a limit of detection at 10.8 fg mL –1 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗