Wilaiwan Chouyyok

Phosphate Removal by Anion Binding on Functionalized Nanoporous Sorbents

Phosphate was captured from aqueous solutions by cationic metal-EDA complexes anchored inside mesoporous silica MCM-41 supports (Cu(II)-EDA-SAMMS and Fe(III)-EDA-SAMMS). Fe-EDA-SAMMS was more effective at capturing phosphate than the Cu-EDA-SAMMS and was further studied for matrix effects (e.g., pH, ionic strength, and competing anions) and sorption performance (e.g., capacity and rate). The adsorption of phosphate was highly pH dependent; it increased with increasing pH from 1.0 to 6.5, and decreased above pH 6.5. The adsorption was affected by high ionic strength (0.1 M of NaCl). In the presence of 1000-fold molar excess of chloride and nitrate anions, phosphate removal by Fe-EDA-SAMMS was not affected. Slight, moderate and large impacts were seen with bicarbonate, sulfate, and citrate anions, respectively. The phosphate adsorption data on Fe-EDA-SAMMS agreed well with the Langmuir model with the estimated maximum capacity of 43.3 mg/g. The material displayed rapid sorption rate (99% of phosphate removal within 1 min) and lowering the phosphate content to approximately 10 microg/L of phosphorus, which is lower than the EPAs established freshwater contaminant level for phosphorus (20 microg/L).

Functionalized Nanoporous Silica for the Removal of Heavy Metals from Biological Systems: Adsorption and Application

Surface-functionalized nanoporous silica, often referred to as self-assembled monolayers on mesoporous supports (SAMMS), has previously demonstrated the ability to serve as very effective heavy metal sorbents in a range of aquatic and environmental systems, suggesting that they may be advantageously utilized for biomedical applications such as chelation therapy. Herein we evaluate surface chemistries for heavy metal capture from biological fluids, various facets of the materials biocompatibility, and the suitability of these materials as potential therapeutics. Of the materials tested, thiol-functionalized SAMMS proved most capable of removing selected heavy metals from biological solutions (i.e., blood, urine, etc.) Consequentially, thiol-functionalized SAMMS was further analyzed to assess the materials performance under a number of different biologically relevant conditions (i.e., variable pH and ionic strength) to gauge any potentially negative effects resulting from interaction with the sorbent, such as cellular toxicity or the removal of essential minerals. Additionally, cellular uptake studies demonstrated no cell membrane permeation by the silica-based materials generally highlighting their ability to remain cellularly inert and thus nontoxic. The results show that organic ligand functionalized nanoporous silica could be a valuable material for a range of detoxification therapies and potentially other biomedical applications.

Selective removal of copper (II) from natural waters by nanoporous sorbents functionalized with chelating diamines

Copper has been identified as a pollutant of concern by the U.S. Environmental Protection Agency (EPA) because of its widespread occurrence and toxic impact in the environment. Three nanoporous sorbents containing chelating diamine functionalities were evaluated for Cu(2+) adsorption from natural waters: ethylenediamine functionalized self-assembled monolayers on mesoporous supports (EDA-SAMMS), ethylenediamine functionalized activated carbon (AC-CH(2)-EDA), and 1,10-phenanthroline functionalized mesoporous carbon (Phen-FMC). The pH dependence of Cu(2+) sorption, Cu(2+) sorption capacities, rates, and selectivity of the sorbents were determined and compared with those of commercial sorbents (Chelex-100 ion-exchange resin and Darco KB-B activated carbon). All three chelating diamine sorbents showed excellent Cu(2+) removal (approximately 95-99%) from river water and seawater over the pH range 6.0-8.0. EDA-SAMMS and AC-CH(2)-EDA demonstrated rapid Cu(2+) sorption kinetics (minutes) and good sorption capacities (26 and 17 mg Cu/g sorbent, respectively) in seawater, whereas Phen-FMC had excellent selectivity for Cu(2+) over other metal ions (e.g., Ca(2+), Fe(2+), Ni(2+), and Zn(2+)) and was able to achieve Cu below the EPA recommended levels for river and sea waters.

Manganese doping of magnetic iron oxide nanoparticles: tailoring surface reactivity for a regenerable heavy metal sorbent.

A method for tuning the analyte affinity of magnetic, inorganic nanostructured sorbents for heavy metal contaminants is described. The manganese-doped iron oxide nanoparticle sorbents have a remarkably high affinity compared to the precursor material. Sorbent affinity can be tuned toward an analyte of interest simply by adjustment of the dopant quantity. The results show that following the Mn doping process there is a large increase in affinity and capacity for heavy metals (i.e., Co, Ni, Zn, As, Ag, Cd, Hg, and Tl). Capacity measurements were carried out for the removal of cadmium from river water and showed significantly higher loading than the relevant commercial sorbents tested for comparison. The reduction in Cd concentration from 100 ppb spiked river water to 1 ppb (less than the EPA drinking water limit of 5 ppb for Cd) was achieved following treatment with the Mn-doped iron oxide nanoparticles. The Mn-doped iron oxide nanoparticles were able to load ~1 ppm of Cd followed by complete stripping and recovery of the Cd with a mild acid wash. The Cd loading and stripping is shown to be consistent through multiple cycles with no loss of sorbent performance.

Collection of Lanthanides and Actinides from Natural Waters with Conventional and Nanoporous Sorbents

Effective collection of trace-level lanthanides and actinides is advantageous for recovery and recycling of valuable resources, environmental remediation, chemical separations, and in situ monitoring. Using isotopic tracers, we have evaluated a number of conventional and nanoporous sorbent materials for their ability to capture and remove selected lanthanides (Ce and Eu) and actinides (Th, Pa, U, and Np) from fresh and salt water systems. In general, the nanostructured materials demonstrated a higher level of performance and consistency. Nanoporous silica surface modified with 3,4-hydroxypyridinone provided excellent collection and consistency in both river water and seawater. The MnO(2) materials, in particular the high surface area small particle material, also demonstrated good performance. Other conventional sorbents typically performed at levels below the nanostructured sorbents and demonstrate a larger variability and matrix dependency.

Novel sorbents for removal of gadolinium-based contrast agents in sorbent dialysis and hemoperfusion: preventive approaches to nephrogenic systemic fibrosis

UNLABELLEDnMany forms of organocomplexed gadolinium (Gd) contrast agents have recently been linked to a debilitating and a potentially fatal skin disease called nephrogenic systemic fibrosis (NSF) in patients with renal failure. Free Gd released from these complexes via transmetallation is believed to be the most important trigger for NSF. In this work, nanostructure silica materials that have been functionalized with 1-hydroxy-2-pyridinone (1,2-HOPO-SAMMS) have been evaluated for selective and effective removal of both free and chelated Gd (gadopentetate dimeglumine and gadodiamide) from dialysate and blood. 1,2-HOPO SAMMS has high affinity, rapid removal rate, and large sorption capacity for both free and chelated Gd, properties that are far superior to those of activated carbon and zirconium phosphate currently used in the state-of-the-art sorbent dialysis and hemoperfusion systems. The SAMMS-based sorbent dialysis and hemoperfusion will potentially provide an effective and predicable strategy for removing the Gd from patients with impaired renal function after Gd exposure, thus allowing for the continued use of Gd-based contrast magnetic resonance imaging while removing the risk of NSF.nnnFROM THE CLINICAL EDITORnChelated gadolinium (Gd) contrast agents have been linked to a debilitating disease called nephrogenic systemic fibrosis (NSF) in patients with renal failure. Free Gd+(3) released from the contrast agents is believed to be the trigger for NSF. In this work, functionalized nanostructured silica materials were evaluated for removal of both free and chelated gadolinium both from dialysate and blood. The new method demonstrated a rapid removal rate and large sorption capacity, and overall was far superior to currently used state-of-the-art sorbent dialysis and hemoperfusion systems.

Thiol−Ene Induced Diphosphonic Acid Functionalization of Superparamagnetic Iron Oxide Nanoparticles

Multifunctional organic molecules represent an interesting challenge for nanoparticle functionalization due to the potential for undesirable interactions between the substrate material and the variable functionalities, making it difficult to control the final orientation of the ligand. In the present study, UV-induced thiol-ene click chemistry has been utilized as a means of directed functionalization of bifunctional ligands on an iron oxide nanoparticle surface. Allyl diphosphonic acid ligand was covalently deposited on the surface of thiol-presenting iron oxide nanoparticles via the formation of a UV-induced thioether. This method of thiol-ene click chemistry offers a set of reaction conditions capable of controlling the ligand deposition and circumventing the natural affinity exhibited by the phosphonic acid moiety for the iron oxide surface. These claims are supported via a multimodal characterization platform which includes thermogravimetric analysis, X-ray photoelectron spectroscopy, and metal contact analysis and are consistent with a properly oriented, highly active ligand on the nanoparticle surface. These experiments suggest thiol-ene click chemistry as both a practical and generally applicable strategy for the directed deposition of multifunctional ligands on metal oxide nanoparticle surfaces.

Improved explosive collection and detection with rationally assembled surface sampling materials

Sampling and detection of trace explosives are critical steps in the analytical process necessary for modern transportation safety. In this work we have explored some of the fundamental aspects that influence collection and detection of trace levels of explosive residues from surfaces. We compared the analyte-release performance of standard muslin sampling swipes to that of rationally assembled fiberglass cloth, and used thermal-desorption ion mobility spectroscopy for detection. This collection–detection system is widely used for analyzing the trace chemical residues. The fiberglass cloth was chemically modified by covalently bonding phenyl-functional groups to the surface. The rationally assembled sampling materials provide significantly performance improvements over standard muslin sampling materials for detection of TNT, NG, RDX, TATP, and PETN. The phenyl-functionalized fiberglass swipes showed over 10 times greater TNT release, compared to muslin sampling swipes, as well as improved response and repeatability after multiple uses of the same swipe. The improved TNT release from the functionalized-fiberglass swipes resulted in significantly improved detection limits over muslin. To better understand the improvement offered by the phenyl-functionalized fiberglass, several commercially available fiberglass materials, each offering specific characteristics, were also compared, allowing several physical and chemical properties to be systematically explored to determine their influence on performance. These results are relevant to improving the detection of other explosive compounds, and potentially to a wider range of chemical sampling from surfaces.

Rapid extraction and assay of uranium from environmental surface samples

Environmental sampling to detect trace nuclear signatures is key component of international nuclear treaty enforcement. Herein, we explored rapid chemical extraction methods coordinated with measurement systems to provide faster, simpler assay of low level uranium from environmental samples. A key problem with the existing analytical method for processing environmental surface samples is the requirement for complete digestion of sample and sampling material. This is a time-consuming and labor-intensive process that limits laboratory throughput, elevates analytical costs, and increases background levels. Promising extraction methods were competitively evaluated for their potential to quickly and efficiently remove different chemical species of uranium from standard surface sampling material. A preferred combination of carbonate and peroxide solutions is shown to give rapid and complete form of uranyl compound extraction and dissolution. This simplified and accelerated extraction process is demonstrated with standard sampling material to be compatible with standard inductive coupled plasma mass spectrometry methods for uranium isotopic assay as well as rapid screening techniques such as X-ray fluorescence (XRF). Rapid extraction of the entire swipe is shown to allow efficient XRF assay of all collected material for simple, fast, nanogram-level XRF assay of the sample. The new methods have direct application in the support of nuclear safeguards treaty enforcement efforts as well as health and safety monitoring. The general approach described may have applications beyond uranium to other trace analytes of nuclear forensic interest (e.g., rare earth elements and plutonium) as well as heavy metals for environmental and industrial hygiene monitoring.