Kathryn M. L. Taylor-Pashow

Postsynthetic modifications of iron-carboxylate nanoscale metal-organic frameworks for imaging and drug delivery.

Fe(III)-carboxylate nanoscale metal-organic frameworks (NMOFs) with the MIL-101 structure were synthesized using a solvothermal technique with microwave heating. The approximately 200 nm particles were characterized using a variety of methods, including SEM, PXRD, nitrogen adsorption measurements, TGA, and EDX. By replacing a percentage of the bridging ligand (terephthalic acid) with 2-amino terephthalic acid, amine groups were incorporated into the framework to provide sites for covalent attachment of biologically relevant cargoes while still maintaining the MIL-101 structure. In proof-of-concept experiments, an optical contrast agent (a BODIPY dye) and an ethoxysuccinato-cisplatin anticancer prodrug were successfully incorporated into the Fe(III)-carboxylate NMOFs via postsynthetic modifications of the as-synthesized particles. These cargoes are released upon the degradation of the NMOF frameworks, and the rate of cargo release was controlled by coating the NMOF particles with a silica shell. Potential utility of the new NMOF-based nanodelivery vehicles for optical imaging and anticancer therapy was demonstrated in vitro using HT-29 human colon adenocarcinoma cells.

Hybrid nanomaterials for biomedical applications

Hybrid nanomaterials, composed of both inorganic and organic components, have recently been examined as promising platforms for imaging and therapeutic applications. This unique class of nanomaterials can not only retain beneficial features of both the inorganic and organic components, but also provides the ability to systematically tune the properties of the hybrid material through the combination of functional components. This feature article will summarize recent advances in the design and synthesis of hybrid nanomaterials and their applications in biological and biomedical areas. The hybrid nanomaterials to be discussed fall into two main categories, silica based materials and nanoscale metal-organic frameworks. Their applications as imaging contrast agents and nanotherapeutics will be highlighted.

Multifunctional Mesoporous Silica Nanospheres with Cleavable Gd(III) Chelates as MRI Contrast Agents: Synthesis, Characterization, Target-Specificity, and Renal Clearance

Mesoporous silica nanospheres (MSNs) are a promising material for magnetic resonance imaging (MRI) contrast agents. In this paper multifunctional MSNs with cleavable Gd(III) chelates are synthesized and characterized, and their applicability as MRI contrast agents is demonstrated both in vitro and in vivo. The MSNs contain Gd(III) chelates that are covalently linked via a redox-responsive disulfide moiety. The MSNs are further functionalized with polyethylene glycol (PEG) and an anisamide ligand to improve their biocompatibility and target specificity. The effectiveness of MSNs as an MRI imaging contrast agent and their targeting ability are successfully demonstrated in vitro using human colon adenocarcinoma and pancreatic cancer cells. Finally, the capability of this platform as an in vivo MRI contrast agent is tested using a 3T scanner. The Gd(III) chelate was quickly cleaved by the blood pool thiols and eliminated through the renal excretion pathway. Further tuning of the Gd(III) chelate release kinetics is needed before the MSN system can be used as target-specific MRI contrast agents in vivo.

Mesoporous Silica Nanoparticles with Co-Condensed Gadolinium Chelates for Multimodal Imaging.

Several mesoporous silica nanoparticle (MSN) contrast agents have been synthesized using a co-condensation method to incorporate two different Gd3+ complexes at very high loadings (15.5–28.8 wt %). These MSN contrast agents, with an MCM-41 type pore structure, were characterized using a variety of methods including SEM and TEM, nitrogen adsorption measurements, thermogravimetric analysis (TGA), direct current plasma (DCP) spectroscopy, and powder X-ray diffraction (PXRD). The magnetic resonance (MR) relaxivities of these contrast agents were determined using a 3 T MR scanner. The r1 relaxivities of these nanoparticles range from 4.1 to 8.4 mM−1s−1 on a per Gd basis. Additionally, the MSN particles were functionalized with an organic fluorophore and cancer cell targeting peptide to allow for demonstration of both the optical and MR contrast enhancing capabilities in vitro.

Advances in Inorganic and Hybrid Ion Exchangers

Ion-exchange materials have been used in industrial applications for well over one hundred years. Since the introduction of polymer based ion exchangers more than seventy years ago, the use of these materials has grown and has dominated the commercial market for more than half a century. Inorganic and hybrid inorganic/organic materials continue to garner attention due to their chemical and radiation stability and effectiveness over wide range of conditions. Driving these research efforts is the desire to improve the selectivity and increase the capacity of the ion-exchanger for a particular application. This article presents a review of the literature detailing the syntheses, characterization, and ion-exchange performance of inorganic and hybrid ion-exchange materials.

Development of an Improved Titanate-Based Sorbent for Strontium and Actinide Separations under Strongly Alkaline Conditions

High-level nuclear waste produced from fuel reprocessing operations at the Savannah River Site (SRS) requires pretreatment to remove 134,137Cs, 90Sr, and alpha-emitting radionuclides (i.e., actinides) prior to disposal onsite as low level waste. The separation processes at SRS include the sorption of 90Sr and alpha-emitting radionuclides onto monosodium titanate (MST) and caustic side solvent extraction of 137Cs. The MST and separated 137Cs is encapsulated along with the sludge fraction of high-level waste (HLW) into a borosilicate glass waste form for eventual entombment at a federal repository. The predominant alpha-emitting radionuclides in the highly alkaline waste solutions include plutonium isotopes 238Pu, 239Pu, and 240Pu; 237Np; and uranium isotopes, 235U and 238U. This article describes recent results evaluating the performance of an improved sodium titanate material that exhibits increased removal kinetics and capacity for 90Sr and alpha-emitting radionuclides compared to the current baseline material, MST.

Laboratory Scoping Tests Of Decontamination Of Hanford Waste Treatment Plant Low Activity Waste Off-Gas Condensate Simulant

The Hanford Waste Treatment and Immobilization Plant (WTP) Low Activity Waste (LAW) vitrification facility will generate an aqueous condensate recycle stream (LAW Off-Gas Condensate) from the off-gas system. The baseline plan for disposition of this stream is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation and recycled to the LAW vitrification facility again. Alternate disposition of this stream would eliminate recycling of problematic components, and would enable de-coupled operation of the LAW melter and the Pretreatment Facilities. Eliminating this stream from recycling within WTP would also decrease the LAW vitrification mission duration and quantity of glass waste. This LAW Off-Gas Condensate stream contains components that are volatile at melter temperatures and are problematic for the glass waste form. Because this stream recycles within WTP, these components accumulate in the Condensate stream, exacerbating their impact on the number of LAW glass containers that must be produced. Approximately 32% of the sodium in Supplemental LAW comes from glass formers used to make the extra glass to dilute the halides to acceptable concentrations in the LAW glass, and diverting the stream reduces the halides in the recycled Condensate and is a key outcome of this work. Additionally, under possible scenarios where the LAW vitrification facility commences operation prior to the WTP Pretreatment facility, identifying a disposition path becomes vitally important. This task seeks to examine the potential treatment of this stream to remove radionuclides and subsequently disposition the decontaminated stream elsewhere, such as the Effluent Treatment Facility (ETF), for example. The treatment process envisioned is very similar to that used for the Actinide Removal Process (ARP) that has been operating for years at the Savannah River Site (SRS), and focuses on using mature radionuclide removal technologies that are also compatible with longterm tank storage and immobilization methods. For this new application, testing is needed to demonstrate acceptable treatment sorbents and precipitating agents and measure decontamination factors for additional radionuclides in this unique waste stream. The origin of this LAW Off-Gas Condensate stream will be the liquids from the Submerged Bed Scrubber (SBS) and the Wet Electrostatic Precipitator (WESP) from the LAW melter off-gas system. The stream is expected to be a dilute salt solution with near neutral pH, and will likely contain some insoluble solids from melter carryover. The soluble components are expected to be mostly sodium and ammonium salts of nitrate, chloride, and fluoride. This stream has not been generated yet and will not be available until the WTP begins operation, but a simulant has been produced based on models, calculations, and comparison with pilot-scale tests. One of the radionuclides that is volatile and expected to be in high concentration in this LAW Off-Gas Condensate stream is Technetium-99 ({sup 99}Tc). Technetium will not be removed from the aqueous waste in the Hanford WTP, and will primarily end up immobilized in the LAW glass by repeated recycle of the off-gas condensate into the LAW melter. Other radionuclides that are also expected to be in appreciable concentration in the LAW Off-Gas Condensate are {sup 129}I, {sup 90}Sr, {sup 137}Cs, and {sup 241}Am. This report discusses results of preliminary radionuclide decontamination testing of the simulant. Testing examined use of Monosodium Titanate (MST) to remove {sup 90}Sr and actinides, inorganic reducing agents for {sup 99}Tc, and zeolites for {sup 137}Cs. Test results indicate that excellent removal of {sup 99}Tc was achieved using Sn(II)Cl{sub 2} as a reductant, coupled with sorption onto hydroxyapatite, even in the presence of air and at room temperature. This process was very effective at neutral pH, with a Decontamination Factor (DF) >577 in two hours. It was less effective at alkaline pH. Conversely, removal of the cesium was more effective at alkaline pH, with a DF of 17.9. As anticipated, ammonium ion probably interfered with the Ionsiv®a IE-95 zeolite uptake of {sup 137}Cs. Although this DF of {sup 137}Cs was moderate, additional testing is expected to identify more effective conditions. Similarly, Monosodium Titanate (MST) was more effective at alkaline pH at removing Sr, Pu, and U, with a DF of 319, 11.6, and 10.5, respectively, within 24 hours. Actually, the Ionsiv® IE-95, which was targeting removal of Cs, was also moderately effective for Sr, and highly effective for Pu and U at alkaline pH. The only deleterious effect observed was that the chromium co-precipitates with the {sup 99}Tc during the SnCl{sub 2} reduction. This effect was anticipated, and would have to be considered when managing disposition paths of this stream. Results of this separation testing indicate that sorption/precipitation was a viable concept and has the potential to decontaminate the stream. All radionuclides were at least partially removed by one or more of the materials tested. Based on the results, a possible treatment scenario could involve the use of a reductive precipitation agent (SnCl{sub 2}) and sorbent at neutral pH to remove the Tc, followed by pH adjustment and the addition of zeolite (Ionsiv® IE-95) to remove the Cs, Sr, and actinides. Addition of MST to remove Sr and actinides may not be needed. Since this was an initial phase of testing, additional tasks to improve separation methods were expected to be identified. Primarily, further testing is needed to identify the conditions for the decontamination process. Once these conditions are established, follow-on tasks likely include evaluation and testing of applicable solid-liquid separation technologies, slurry rheology measurements, composition variability testing and evaluations, corrosion and erosion testing, slurry storage and immobilization investigations, and decontaminated LAW Off-Gas Condensate evaporation and solidification.

Characterization of Modified Monosodium Titanate – An Improved Sorbent for Strontium and Actinide Separations

High-level nuclear waste produced from fuel reprocessing operations at the Savannah River Site requires pretreatment to remove 134,137Cs, 90Sr, and alpha-emitting radionuclides (i.e., actinides) prior to disposal onsite as low level waste. An inorganic sorbent, monosodium titanate, is currently used to remove 90Sr and alpha-emitting radionuclides, while a caustic-side solvent extraction process is used for removing 134,137Cs. A new peroxotitanate material has recently been developed and has shown increased removal kinetics and capacity for 90Sr and alpha-emitting radionuclides compared to the current baseline material. This article describes recent results focused on further characterization of this material.

Tc removal from the waste treatment and immobilization plant low-activity waste vitrification off-gas recycle

ABSTRACT Vitrification of Low Activity Waste in the Hanford Waste Treatment and Immobilization Plant generates a condensate stream from the off-gas processes. Components in this stream are partially volatile and accumulate to high concentrations through recycling, which impacts the waste glass loading and facility throughput. The primary radionuclide that vaporizes and accumulates in the stream is 99Tc. This program is investigating Tc removal via reductive precipitation with stannous chloride to examine the potential for diverting this stream to an alternate disposition path. Research has shown stannous chloride to be effective, and this paper describes results of recent experiments performed to further mature the technology.

In vitro biological response of micro‐ and nano‐sized monosodium titanates and titanate–metal compounds

Previous studies report that microsized monosodium titanates (MSTs) deliver metal ions and species to mammalian cells and bacteria with cell-specific and metal-specific effects. In this study, we explored the use of MST and a new synthesized nanosized monosodium titanate (nMST) to deliver gold(III), cisplatin, or platinum(IV) to two human cell lines with different population doubling times, in vitro. The effect was measured using a fluorescent mitochondrial activity assay (CellTiter-Blue(®) Assay). This fluorescence assay was implemented to mitigate optical density measurement errors owing to particulate titanate interference and allowed for the studies to be extended to higher titanate concentrations than previously possible. Overall, native MST significantly (p < 0.05) decreased mitochondrial activity of both cell types by 50% at concentrations of >50 mg/L. Native nMST significantly suppressed the rapidly dividing cell line (by 50%) over untreated cultures, but had no effect on the more slowly dividing cells. For both cell types, increased titanate concentrations resulted in increased effects from delivered metals. However, there was no difference in the effect of metal delivered from micro- versus nano-sized MST.