Chemical modification of nanoparticles or particlelike systems is ubiquitously being used to facilitate specific pharmaceutical functionalities or physicochemical attributes of nanocrystals, proteins, enzymes, or other particlelike systems. Often the modification process is incomplete and the functional activity of the product depends upon the distribution of functional ligands among the different particles in the system. Here, the distribution function describing the spread of ligands in particlelike systems undergoing partial modification reactions is derived and validated against a conjugated enzyme model system by use of matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF). The distribution function is shown to be applicable to describe the distribution of ligands in a wide range of particlelike systems (such as enzymes, dendrimers, or inorganic nanocrystals) and is used to establish guidelines for the synthesis of uniformly modified particle systems even at low reaction efficiencies.

Poly(propylene sulfide) nanoparticles (<150 nm) have been synthesized by an anionic, ring-opening emulsion polymerization. Upon exposure to parts per million (ppm) levels of oxidizing agent (NaOCl), hydrophobic polysulfide particles are oxidized to hydrophilic polysulfoxides and polysulfones. Utilizing this mechanism, the encapsulation of hydrophobic molecular cargo, including Nile red and Reichardt's dye, within polysulfide nanoparticles has been characterized by a variety of microscopic and spectroscopic methods and its release demonstrated via chemical oxidation. Moreover, release of cargo has been enzymatically driven by oxidoreductase enzymes such as chloroperoxidase and myeloperoxidase in the presence of low concentrations of sodium chloride (200 mM) and hydrogen peroxide (500 μM). This oxidation-driven mechanism holds promise for controlled encapsulation and release of a variety of hydrophobic cargos.

In the advancement of green syntheses and sustainable reactions, enzymatic biocatalysis offers extremely high reaction rates and selectivity that goes far beyond the reach of chemical catalysts; however, these enzymes suffer from typical environmental constraints, e.g. operational temperature, pH and tolerance to oxidative environments. A common hydrolase enzyme, diisopropylfluorophosphatase (DFPase, EC 3.1.8.2), has demonstrated a pronounced efficacy for the hydrolysis of a variety of substrates for potential toxin remediation, but suffers from the aforementioned limitations. As a means to enhance DFPase’s stability in oxidative environments, enzymatic covalent immobilization within the polymeric matrix of poly(propylene sulfide) (PPS) nanoparticles was performed. By modifying the enzyme’s exposed lysine residues via thiolation, DFPase is utilized as a comonomer/crosslinker in a mild emulsion polymerization. The resultant polymeric polysulfide shell acts as a ‘sacrificial barrier’ by first oxidizing to polysulfoxides and polysulfones, rendering DFPase in an active state. DFPase–PPS nanoparticles thus retain activity upon exposure to as high as 50 parts per million (ppm) of hypochlorous acid (HOCl), while native DFPase is observed as inactive at 500 parts per billion (ppb). This trend is also confirmed by enzyme-generated (chloroperoxidase (CPO), EC 1.11.1.10) reactive oxygen species (ROS) including both HOCl (3 ppm) and ClO2 (100 ppm).

It has previously been demonstrated that damaged arterial tissue can be acutely modified with proteinreactive polyethylene glycol (PEG) to block undesirable platelet deposition. This concept might be expanded by employing PEG-biotin and its strong interaction with avidin for site-specific targeted delivery. Toward this end, cultured endothelial cells (ECs) were surface modified with PEG-biotin and the available biotin was quantified with flow cytometry. NeutrAvidin-coated microspheres and PEG-biotin modified ECs with NeutrAvidin as a bridging molecule were delivered under arterial shear stress to PEG-biotin modified ECs on a coverslip as well as scrape-damaged bovine carotid arteries. After incubation with a 10 mM solution for 1 min, 8 × 10 7 PEG-biotin molecules/EC were found and persisted for up to 120 h. Perfused microspheres adhered to NHS-PEG-biotin treated bovine carotid arteries with 60 ± 16 microspheres/mm 2 versus 11 ± 4 microspheres/mm 2 for control arteries (p < 0.015). Similarly, 22 ± 5 targeted ECs/mm 2 adhered to NHS-PEG-biotin treated bovine carotid arteries versus 6 ± 2 ECs/mm 2 for control arteries (p < 0.01). The targeting strategy demonstrated here might ultimately find application for drug delivery, gene therapy, or cell therapy where localization to specific labeled vascular regions is desired following catheter-based or surgical procedures.

Evaporation of High Level and Low Activity (HLW & LAW) radioactive wastes for the purposes of radionuclide separation and volume reduction has been conducted at the Savannah River and Hanford Sites for more than forty years. Additionally, the Savannah River Site (SRS) has used evaporators in preparing HLW for immobilization into a borosilicate glass matrix. The Hanford River Protection Project (RPP) is in the process of building the world's largest radioactive waste treatment facility, Waste Treatment Plant (WTP), which will use evaporators to concentrate the liquid waste and plant recycles prior to immobilization into a borosilicate glass matrix. Radioactive waste is evaporated at each site using various evaporator designs (e.g., forced circulation, horizontal bent tube). While the equipment used to evaporate radioactive waste is relatively simple in design, the complexity in the evaporator processes in current service and in those currently in the design stages stems from the heterogeneous nature of the waste and the effects of seemingly minor components (e.g., Si) on the process.Aqueous electrolyte thermodynamic modeling and experiments have been conducted by the SRS Savannah River Technology Center (SRTC) in support of the SRS HLW and Defense Waste Processing Facility (DWPF) Evaporators and the Hanford RPP WTP. After 40 years of successful operation, accumulation of two solid phases (a nitrated aluminosilicate, Na 8 Al 6 Si 6 O 24 (NO 3 ) 2 •4H 2 O and sodium diuranate, Na 2 U 2 O 7 ) developed as an insoluble phase in the Savannah River Site (SRS) 2H evaporator in 1996. The aluminosilicate scale deposit caused the SRS 2-H evaporator to become completely inoperable by October 1999. Accumulation of the sodium diuranate phase on the aluminosilicate scale has caused criticality concerns. Modeling and experiments were conducted to develop a method to control the process chemistry in order to prevent the formation of aluminosilicate deposits in the future.The lessons learned from the development, design, and operation of the SRS waste treatment facilities and the currently operating 242-A Hanford HLW evaporators were applied by SRTC in support of the development and design of the Hanford WTP evaporators. Thermodynamic equilibrium modeling along with solubility and physical property experiments are being conducted to develop process control and flow sheet models. Additionally, lessons learned from the development of an advanced antifoam agent for the SRS vitrification process evaporators are being applied to the testing and development of an antifoam agent for the Hanford WTP evaporators. This paper will discuss the methodologies, results, and achievements of the SRTC evaporator development program that was conducted in support of the SRS and Hanford WTP evaporator processes. The "crosspollination" and application of waste treatment technologies and methods between the Savannah River and Hanford Sites will be highlighted. The "crosspollination" of technologies and methods is expected to benefit the Departm...