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Glen E Fryxell

Publications and source records attributed to Glen E Fryxell.

14 recordsLinked to original sources

Voltammetric analysis of europium at screen-printed electrodes modified with salicylamide self-assembled on mesoporous silica.

Mercury-free sensors for europium (Eu(3+)) assay based on the chemical modification of screen-printed carbon electrodes (SPCEs) with self-assembled salicylamide on mesoporous silica (Sal-SAMMS) have been developed. The preconcentration of Eu(3+) at SAMMS-based sensors utilizes the binding affinity of the salicylamide and Eu(3+), accomplished at open circuit potential without electrolyte and solution de-gassing. Optimal Eu detection was obtained after 3-5 min preconcentration in Eu solution (pH 2-6), electrolysis at -0.9 V for 60 s in a new medium (0.1-0.2 M NH(4)Cl, pH 3.5), followed by a square-wave voltammetric detection of Eu in the same electrolyte. Attributed to the strong covalent bonding of the functional groups on mesoporous silica and silane cross-linking, the SAMMS-modified SPCEs with a built-in 3-electrode system can be re-used for tens of measurements with minimal degradation, enabling the establishment of the calibration curve and lowering the costs. A linear calibration curve was found in the range of 75 to at least 500 ppb Eu(3+) after 5 min preconcentration. The experimental detection limit was 10 ppb after 10 min preconcentration, which can be improved with increased preconcentration time. Reproducibility (% RSD) of 100 ppb Eu(2+) was 10% for a single sensor and 10% for 5 sensors, which can be improved through the precision of sensor manufacturing, in which SAMMS modification can be made in-situ.

Journal Article↗

Synthesis of organically templated nanoporous Tin(II/IV) phosphate for radionuclide and metal sequestration.

Nanoporous tin(II/IV) phosphate materials, with spherical morphology, have been synthesized using cetyltrimethylammonium chloride [CH3(CH2)15N(CH3)3Cl] as the surfactant. The structure of the material is stable at 500 degrees C; however, partial oxidation of the material occurs with redox conversion of Sn2+ to Sn4+, resulting in a mixed Sn(II)/Sn(IV) material. Preliminary batch contact studies were conducted to assess the effectiveness of nanoporous tin phosphate, NP-SnPO, in sequestering redox-sensitive metals and radionuclides, technetium(VII), neptunium(V), thorium(IV), and a toxic metal, chromium(VI), from aqueous matrixes. Results indicate that tin(II) phosphate removed >95% of all contaminants investigated from solution.

Journal Article↗

Functionalized TiO2 nanoparticles for use for in situ anion immobilization.

Anatase particles (40-60 nm) were coated with an organosilane monolayer terminated with an ethylenediamine (EDA) ligand. These functionalized nanoparticles (FNPs) were then treated with an aqueous solution of Cu(II) to create a cationic Cu-EDA complex bound to the nanoparticle surface. Cu(II) and EDA ligand incorporation were confirmed by X-ray photoelectron spectroscopy (XPS) analysis. The Cu(EDA)2 FNP was then studied for its binding affinity for pertechnetate anion from a Hanford groundwater matrix. The Cu(EDA)2 FNP was also evaluated for its injectability into a porous medium for possible application as a subsurface semipermeable reactive barrier. Injection was readily accomplished, and resulted in a highly uniform distribution of the FNP sorbent in the test column.

Adsorption↗

Hygroscopic growth of self-assembled layered surfactant molecules at the interface between air and organic salts.

We report here the self-assembly of surfactant molecules at the interface of air and the hygroscopic quaternary ammonium salt tetrabutylammonium acetate (TBAAc). Homogeneously dissolved surfactant molecules at 100 degrees C self-assemble upon contacting air due to high moisture adsorption by the organic salt when cooling down. Highly ordered lamellar phases with different lattice spacings have been observed when surfactants with various lengths of alkyl chains were used. C(n)TMAB/TBAAc systems showed all-trans conformation of interior methylene carbons and interdigited bilayers with an average CH2 increment of 0.119 nm, while C(n)NH2/TBAAc systems showed trans/gauche mixed conformations of interior methylene carbons and bilayers with an average CH2 increment of 0.247 nm. C(n)NH2s in C(n)NH2/TBAAc formed bilayers through water-mediated intermolecular hydrogen bonds with a water layer thickness of 0.51-0.61 nm. In C(n)TAB/TBAAc, as the head group of C(n)TAB is bigger, the interdigited bilayer thickness (d-spacing) is smaller, because the bigger head groups accommodate enough space for alkyl tails to come in between them.

Journal Article↗

Incorporation of hydroxypyridinone ligands into self-assembled monolayers on mesoporous supports for selective actinide sequestration.

In this study, three isomers of hydroxypyridinones (1,2-HOPO, 3,2-HOPO, and 3,4-HOPO) were attached to self-assembled monolayers on mesoporous silica (SAMMS). The HOPO-SAMMS materials have superior solid adsorbents properties: they do not suffer from solvent swelling; their rigid, open pore structure allows rapid sorption kinetics; their extremely high surface area enables the installation of high functional density; and being silica-based, they are compatible with vitrification into a final vitreous waste form. Kinetics, equilibrium, and selectivity of the adsorptions of actinide on the HOPO-SAMMS at various pH values and in the presence of other metal cations, anions, and competing ligands are reported. Rapid sequestration of U(VI), Np(V), and Pu(IV) was observed. Very little competition from transition metal cations and common species was observed.

Adsorption↗

Actinide sequestration using self-assembled monolayers on mesoporous supports.

Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.

Actinoid Series Elements↗

Hydroxypyridinone functionalized self-assembled monolayers on nanoporous silica for sequestering lanthanide cations.

1,2-Hydroxypyridinone (1,2-HOPO) ligands were installed as self-assembled monolayers on nanoporous silica (MCM-41) to create a superior class of sorbent materials for lanthanide cations. Lanthanides were used as a model system for the radioactive, expensive, and highly hazardous actinides in preliminary screening studies. The ligand properties of the 1,2-HOPO ligand field and the extremely large surface area of MCM-41, coupled with the dense monolayer coating, contribute to the extremely high lanthanide binding capacity of the 1,2-HOPO nanoporous sorbent. At pH 4-5.9, the mass-weighted partition coefficients (Kd) for La, Nd, Eu, and Lu were 354,000, 344,000, 210,800, and 419,800, respectively. The rigid, open pore structure of the silica also allows for very rapid sorption. Being silica-based, the sorbent is compatible with vitrification processing into a final glasseous waste form, for subsequent disposition in a deep geological repository.

Cations↗

Nanostructured electrochemical sensors based on functionalized nanoporous silica for voltammetric analysis of lead, mercury, and copper.

We have successfully developed electrochemical sensors based on functionalized nanostructured materials for voltammetric analysis of toxic metal ions. Glycinylurea self-assembled monolayers on mesoporous silica (Gly-UR SAMMS) were incorporated in carbon paste electrodes for the detection of toxic metal ions such as lead, copper, and mercury based on adsorptive stripping voltammetry (AdSV). The electrochemical sensor yields a linear response at a low ppb level of Pb2+ (i.e., 2.5-50 ppb) after a 2-min preconcentration period, with reproducible measurements (%RSD = 3.5, N = 6) and an excellent detection limit (1 ppb). By exploiting the interfacial functionality of Gly-UR SAMMS, the sensor is selective for the target species, does not require the use of a mercury film, and can be easily regenerated in dilute acid solution. The rigid, open, parallel pore structure, combined with suitable interfacial chemistry of SAMMS, also results in fast analysis times (2-3 min). The nanostructured SAMMS materials enable the development of miniature sensing devices that are compact and low cost, have low energy consumption, and are easily integrated into field-deployable units.

Copper↗

Effects of template and precursor chemistry on structure and properties of mesoporous TiO2 thin films.

Mesoporous TiO2 thin films were synthesized by sol-gel processing using an aqueous-based, inexpensive, and environmentally friendly precursor and cationic surfactants as templates under mild reaction conditions. The films were prepared by spin-coating on glass substrates followed by calcination to remove the surfactant. N2 sorption, X-ray diffraction, and transmission electron microscopy were used to characterize the porosity, pore size, and pore structure before and after calcination. Films were found to have wormlike pore structures after calcination and surface areas on the order of 200 m2/g. These results show that the mesostructure and porosity of the thin films can be controlled by the surfactant template chemistry such as surfactant/Ti ratio, pH, and rate of solvent evaporation.

Adsorption↗

A bifunctional poly(ethylene glycol) silane immobilized on metallic oxide-based nanoparticles for conjugation with cell targeting agents.

A trifluoroethylester-terminal poly(ethylene glycol) (PEG) silane was synthesized and self-assembled on iron oxide nanoparticles. The nanoparticle system thus prepared has the flexibility to conjugate with cell targeting agents via either carboxylic or amine terminal groups for a number of biomedical applications, including magnetic resonance imaging (MRI) and controlled drug delivery. The trifluoroethylester silane was synthesized by modifying a PEG diacid to form the corresponding bistrifluoroethylester (TFEE), followed by a reaction with 3-aminopropyltriethoxysilane (APS). The APS coupled with PEG chains confers the stability of PEG self-assembled monolayers (SAMs) and increases the PEG packing density on nanoparticles by establishing hydrogen bonding between the carbonyl and amine groups present within the monolayer structure. The success of the synthesis of the PEG TEFE silane was confirmed with (1)H NMR and Fourier transform infrared spectroscopy (FTIR). The conjugating flexibility of the PEG TEFE was demonstrated with folic acid that had carboxylic acid groups and amine terminal groups, respectively, and was confirmed by FTIR. TEM analysis showed the well-dispersed nanoparticles before and after they were coated with PEG and folic acid.

Amines↗

Voltammetric detection of lead(II) and mercury(II) using a carbon paste electrode modified with thiol self-assembled monolayer on mesoporous silica (SAMMS).

The anodic stripping voltammetry at a carbon paste electrode modified with thiol terminated self-assembled monolayer on mesoporous silica (SH-SAMMS) provides a new sensor for simultaneous detection of lead (Pb2+) and mercury (Hg2+) in aqueous solutions. The overall analysis involved a two-step procedure: an accumulation step at open circuit, followed by medium exchange to a pure electrolyte solution for the stripping analysis. Factors affecting the performance of the SH-SAMMS modified electrodes were investigated, including electrode activation and regeneration, electrode composition, preconcentration time, electrolysis time, and composition of electrolysis and stripping media. The most sensitive and reliable electrode contained 20% SH-SAMMS and 80% carbon paste. The optimal operating conditions were a sequence with a 2 min preconcentration period, then a 60 s electrolysis period of the preconcentrated species in 0.2 M nitric acid, followed by square wave anodic stripping voltammetry from -1.0 V to 0.6 V in 0.2 M nitric acid. The areas of the peak responses were linear with respect to metal ion concentrations in the ranges of 10-1500 ppb Pb2+ and 20-1600 ppb Hg2+. The detection limits for Pb2+ and Hg2+ were 0.5 ppb Pb2+ and 3 ppb Hg2+ after a 20 min preconcentration period.

Carbon↗