Yongsoon Shin

Bromate removal from water by granular ferric hydroxide (GFH)

The feasibility of granular ferric hydroxide (GFH) for bromate removal from water has been studied. Batch experiments were performed to study the influence of various experimental parameters such as effect of contact time, initial bromate concentration, temperature, pH and effect of competing anions on bromate removal by GFH. The adsorption kinetics indicates that uptake rate of bromate was rapid at the beginning and 75% adsorption was completed in 5 min and equilibrium was achieved within 20 min. The sorption process was well described by pseudo-second-order kinetics. The maximum adsorption potential of GFH for bromate removal was 16.5 mg g(-1) at 25 degrees C. The adsorption data fitted well to the Langmuir model. The increase in OH peak and absence of Br-O bonding in FTIR spectra indicate that ion-exchange was the main mechanism during bromate sorption on GFH. The effects of competing anions and solution pHs (3-9) were negligible. Results of the present study suggest that GFH can be effectively utilized for bromate removal from drinking water.

Hybrid Nanogels for Sustainable Positive Thermosensitive Drug Release

A hybrid nanogel has been developed based on interpenetrating networks of thermosensitive poly(N-isopropylacrylamide) gels and tailored nanoporous silica. A sustainable positive thermo-responsive drug release profile is obtained. When the temperature rises, the polymer gel shrinks, squeezing the drug into the porous channels, and at the same time, opening the pores to the outside media. The drug slowly diffuses out of the porous channels. The overall release rate can be adjusted by changing the composition of the nanogel.

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.

Supercritical Processing of Functionalized Size Selective Microporous Materials

Abstract A supercritical fluid silanation process is applied to effectively functionalize commercial microporous materials without blocking the pore channels. In this approach, supercritical carbon dioxide (SCCO 2 ) is used to deposit mercaptopropyl silane into the microporosity of zeolite beta. The thiol group was subsequently oxidized into sulfonic acid. The size selective catalytic properties of the SCCO 2 modified zeolite compare well with similar materials prepared by an in situ silanation process reported by Jones et al. The active functional groups were delivered to the internal pore surface of the microporous material and remain accessible to molecules that can enter the pore channels. The supercritical process provides an alternative approach to functionalize microporous materials because of the enhanced diffusivity of the functional molecules in the micropore channels and accelerated reaction kinetics. Furthermore, the supercritical process simplifies the materials preparation and may open up new opportunities for commercial zeolites.

Molecular Dynamics Simulations Reveal that Water Diffusion between Graphene Oxide Layers is Slow.

Membranes made of stacked layers of graphene oxide (GO) hold the tantalizing promise of revolutionizing desalination and water filtration if selective transport of molecules can be controlled. We present the findings of an integrated study that combines experiment and molecular dynamics simulation of water intercalated between GO layers. We simulated a range of hydration levels from 1 wt.% to 23.3 wt.% water. The interlayer spacing increased upon hydration from 0.8 nm to 1.1 nm. We also synthesized GO membranes that showed an increase in layer spacing from about 0.7 nm to 0.8 nm and an increase in mass of about 15% on hydration. Water diffusion through GO layers is an order of magnitude slower than that in bulk water, because of strong hydrogen bonded interactions. Most of the water molecules are bound to OH groups even at the highest hydration level. We observed large water clusters that could span graphitic regions, oxidized regions and holes that have been experimentally observed in GO. Slow interlayer diffusion can be consistent with experimentally observed water transport in GO if holes lead to a shorter path length than previously assumed and sorption serves as a key rate-limiting step.

Catalytic templating approaches for three-dimensional hollow carbon/graphene oxide nano-architectures.

We report a catalytic templating method to synthesize well-controlled three-dimensional carbon nano-architectures. Depending on graphene oxide content, the morphology can be systematically tuned from layered composites to 3D hollow structures to microporous materials. The composites with high surface area and high porosity induce a significant enhancement to its capacitance at high current density.

Probing mechanisms for enzymatic activity enhancement of organophosphorus hydrolase in functionalized mesoporous silica

We have previously reported that organophosphorus hydrolase (OPH) can be spontaneously entrapped in functionalized mesoporous silica (FMS) with HOOC- as the functional groups and the entrapped OPH in HOOC-FMS showed enhanced enzyme specific activity. This work is to study the mechanisms that why OPH entrapped in FMS displayed the enhanced activity in views of OPH-FMS interactions using spectroscopic methods. The circular dichroism (CD) spectra show that, comparing to the secondary structure of OPH free in solution, OPH in HOOC-FMS displayed increased alpha-helix/beta-strand transition of OPH with increased OPH loading density. The fluorescence emission spectra of Trp residues were used to assess the tertiary structural changes of the enzyme. There was a 42% increase in fluorescence. This is in agreement with the fact that the fluorescence intensity of OPH was increased accompanying with the increased OPH activity when decreasing urea concentrations in solution. The steady-state anisotropy was increased after OPH entrapping in HOOC-FMS comparing to the free OPH in solution, indicating that protein mobility was reduced upon entrapment. The solvent accessibility of Trp residues of OPH was probed by using acrylamide as a collisional quencher. Trp residues of OPH-FMS had less solvent exposure comparing with free OPH in solution due to its electrostatical binding to HOOC-FMS thereby displaying the increased fluorescence intensity. These results suggest the interactions of OPH with HOOC-FMS resulted in the protein immobilization and a favorable conformational change for OPH in the crowded confinement space and accordingly the enhanced activity.

Alexa Fluor-labeled Fluorescent Cellulose Nanocrystals for Bioimaging Solid Cellulose in Spatially Structured Microenvironments

Methods to covalently conjugate Alexa Fluor dyes to cellulose nanocrystals, at limiting amounts that retain the overall structure of the nanocrystals as model cellulose materials, were developed using two approaches. In the first, aldehyde groups are created on the cellulose surfaces by reaction with limiting amounts of sodium periodate, a reaction well-known for oxidizing vicinal diols to create dialdehyde structures. Reductive amination reactions were then applied to bind Alexa Fluor dyes with terminal amino-groups on the linker section. In the absence of the reductive step, dye washes out of the nanocrystal suspension, whereas with the reductive step, a colored product is obtained with the characteristic spectral bands of the conjugated dye. In the second approach, Alexa Fluor dyes were modified to contain chloro-substituted triazine ring at the end of the linker section. These modified dyes then were reacted with cellulose nanocrystals in acetonitrile at elevated temperature, again isolating material with the characteristic spectral bands of the Alexa Fluor dye. Reactions with Alexa Fluor 546 are given as detailed examples, labeling on the order of 1% of the total glucopyranose rings of the cellulose nanocrystals at dye loadings of ca. 5 μg/mg cellulose. Fluorescent cellulose nanocrystals were deposited in pore network microfluidic structures (PDMS) and proof-of-principle bioimaging experiments showed that the spatial localization of the solid cellulose deposits could be determined, and their disappearance under the action of Celluclast enzymes or microbes could be observed over time. In addition, single molecule fluorescence microscopy was demonstrated as a method to follow the disappearance of solid cellulose deposits over time, following the decrease in the number of single blinking dye molecules with time instead of fluorescent intensity.

The Core–Shell Approach to Formation of Ordered Nanoporous Materials

This work describes a novel core-shell approach for the preparation of ordered nanoporous ceramic materials that involve a self-assembly process at the molecular level using MPEG-b-PDLLA bloack copolymers. This approach provides for rapid self-assembly and structural reorganization at room temperature. Selected MPEG-b-PDLLA block copolymers were synthesized with systematic variation of the chain lengths of the resident hydrophilic and hydrophobic blocks. This allows the micelle size to be systematically varied. Results from this work are used to understand the formation mechanism of nanoporous structures in which the pore size and wall thickness are closely dependent on the size of hydrophobic cores and hydrophilic shells of the block copolymer templates. The core-shell mechanism for nanoporous structure evolution is based on the size and contrasting micellar packing arrangements that are controlled by the copolymer.

Chemical-free growth of metal nanoparticles on graphene oxide sheets under visible light irradiation

In the presence of silver or gold ions, visible light irradiation (> 420 nm) induces the formation of metal nanoparticles on graphene (GO) sheets without the need of any chemical reducing reagents. GO sheets serve as not only a good substrate for dispersion of metal nanoparticles but also a self-reactive material itself for the photo-induced reduction of metal ions.