Gyoung Gug Jang

Scalable production of microbially mediated zinc sulfide nanoparticles and application to functional thin films

A series of semiconducting zinc sulfide (ZnS) nanoparticles were scalably, reproducibly, controllably and economically synthesized with anaerobic metal-reducing Thermoanaerobacter species. These bacteria reduced partially oxidized sulfur sources to sulfides that extracellularly and thermodynamically incorporated with zinc ions to produce sparingly soluble ZnS nanoparticles with ∼5nm crystallites at yields of ∼5gl(-1)month(-1). A predominant sphalerite formation was facilitated by rapid precipitation kinetics, a low cation/anion ratio and a higher zinc concentration compared to background to produce a naturally occurring hexagonal form at the low temperature, and/or water adsorption in aqueous conditions. The sphalerite ZnS nanoparticles exhibited narrow size distribution, high emission intensity and few native defects. Scale-up and emission tunability using copper doping were confirmed spectroscopically. Surface characterization was determined using Fourier transform infrared and X-ray photoelectron spectroscopies, which confirmed amino acid as proteins and bacterial fermentation end products not only maintaining a nano-dimensional average crystallite size, but also increasing aggregation. The application of ZnS nanoparticle ink to a functional thin film was successfully tested for potential future applications.

Size tunable elemental copper nanoparticles: extracellular synthesis by thermoanaerobic bacteria and capping molecules

Bimodal sized elemental copper (Cu) nanoparticles (NPs) were synthesized from inexpensive oxidized copper salts by an extracellular metal-reduction process using anaerobic Thermoanaerobacter sp. X513 bacteria in aqueous solution. The bacteria nucleate NPs outside of the cell, and they control the Cu2+ reduction rate to form uniform crystallites with an average diameter of 1.75 ± 0.46 μm after 3 days incubation. To control the size and enhance the air stability of Cu NPs, the reaction mixtures were supplemented with nitrilotriacetic acid as a chelator, and the surfactant capping agents oleic acid, oleylamine, ascorbic acid, or L-cysteine. Time-dependent UV-visible absorption measurements and XPS studies indicated well-suspended, bimodal colloidal Cu NPs (70–150 and 5–10 nm) with extended air-stability up to 300 min and stable Cu NP film surfaces with 14% oxidation after 20 days. FTIR spectroscopy suggested that these capping agents were effectively adsorbed on the NP surface providing oxidation resistance under aqueous and dry conditions. Compared to previously reported Cu NP syntheses, this biological process substantially reduced the requirement for hazardous organic solvents and chemical reducing agents, while reducing the levels of Cu oxide impurities in the product. This process was highly reproducible and scalable from 0.01 to 1 L batches.

Rate-Limited Electroless Gold Thin Film Growth: A Real-Time Study

Time-resolved, in situ spectroscopy of electroless (EL) gold (Au) films combined with electron microscopy showed that the deposition rate increased up to two-fold on surfaces swept by the bulk flow of adjacent fluid at Reynolds numbers less than 1.0, compared to batch immersion. Deposition rates from 5.0 to 9.0 nm/min and thicknesses of the EL Au film from 20 to 100 nm, respectively, increased predictably with flow rate at conditions when the deposition was limited primarily by Fickian diffusion. Time-frames were identified for metal island nucleation, growth, and subsequent film development during EL Au deposition by real-time UV-visible spectroscopy of photoluminescence (PL) and surface plasmon features of nanoscale metal deposits. Film thicknesses measured by scanning electron microscopy and X-ray photoelectron spectroscopy paired with real-time optical spectroscopy of kinetic aspects of plasmon and PL optical features indicated that Au film deposition on surfaces swept by a steady flow of adjacent fluid can be primarily diffusion limited.

In situ capping for size control of monochalcogenide (ZnS, CdS and SnS) nanocrystals produced by anaerobic metal-reducing bacteria

Metal monochalcogenide quantum dot nanocrystals of ZnS, CdS and SnS were prepared by anaerobic, metal-reducing bacteria using in situ capping by oleic acid or oleylamine. The capping agent preferentially adsorbs on the surface of the nanocrystal, suppressing the growth process in the early stages, thus leading to production of nanocrystals with a diameter of less than 5 nm.

Superhydrophobic and superhydrophilic surface-enhanced separation performance of porous inorganic membranes for biomass-to-biofuel conversion applications

ABSTRACT A new class of porous membranes is introduced to provide unique separation mechanisms by surface interactions and capillary condensation. High-performance architectural surface selective (HiPAS) membranes were designed for high perm-selective flux and high-temperature tolerance for hot vapor processing and liquid processing. Due to surface-enhanced selectivity, larger-fluxes were achieved by utilizing larger pore sizes (~8 nm for vapor phase and micron-sized pores for liquid phase separations). This article describes a membrane-based separation concept for biomass conversion pathways and demonstrates the initial data for selective permeation of toluene–water and toluene–phenol–water relevant to biofuel processing.

The anti-soiling performance of highly reflective superhydrophobic nanoparticle-textured mirrors

The anti-soiling (AS) performance of solar mirrors coated with a highly transparent, superhydrophobic nanoparticle-textured coating has been characterized. The AS coatings were created on the mirror surface by depositing nano-textured silica nanoparticle layers of ∼250 nm thickness using a draw-down coating process, followed by fluorination of the nanoparticles in a molecular vapor deposition process. Highly uniform surface features of the AS-coated mirrors (20 × 30 cm2, no measurable loss in specular reflectance, and water contact angle >165°) provided an outstanding AS performance. A 4× reduction in the rate of dust accumulation as determined by gravimetric measurement of the accumulated dust on coated versus uncoated mirrors was observed. Additional evidence of a significant reduction in soiling rate was determined during measurements of specular reflectance in an outdoor environment test. The adhesion force between a model sand particle and nano-textured coatings in the hydrophobic to superhydrophobic range was also studied. A dramatic decrease in adhesive force acting on the particle was observed with increasing surface hydrophobicity. The results align well with the observed dust accumulation on the AS-coated mirrors. The AS-coated mirror maintains a high reflectivity by shedding dust and resisting dust accumulation, providing a potential benefit when applied to mirrors in the solar field of a concentrated solar power generation plant.

Improved ZnS nanoparticle properties through sequential NanoFermentation

Sequential NanoFermentation (SNF) is a novel process which entails sparging microbially produced gas containing H2S from a primary reactor through a concentrated metal-acetate solution contained in a secondary reactor, thereby precipitating metallic sulfide nanoparticles (e.g., ZnS, CuS, or SnS). SNF holds an advantage over single reactor nanoparticle synthesis strategies, because it avoids exposing the microorganisms to high concentrations of toxic metal and sulfide ions. Also, by segregating the nanoparticle products from biological materials, SNF avoids coating nanoparticles with bioproducts that alter their desired properties. Herein, we report the properties of ZnS nanoparticles formed from SNF as compared with ones produced directly in a primary reactor (i.e., conventional NanoFermentation, or “CNF”), commercially available ZnS, and ZnS chemically synthesized by bubbling H2S gas through a Zn-acetate solution. The ZnS nanoparticles produced by SNF provided improved optical properties due to their smaller crystallite size, smaller overall particle sizes, reduced biotic surface coatings, and reduced structural defects. SNF still maintained the advantages of NanoFermentation technology over chemical synthesis including scalability, reproducibility, and lower hazardous waste burden.

Electron optics of nanoplasmonic metamaterials in bio/opto theranostics

Opto-electronic coupling of plasmonic nano-antennas in the near infrared water window in vitro and in vivo is of growing interest for imaging contrast agents, spectroscopic labels and rulers, biosensing, drug-delivery, and optoplasmonic ablation. Metamaterials composed of nanoplasmonic meta-atoms offer improved figures of merit in many applications across a broader spectral window. Discrete and coupled dipole approximations effectively describe localized and coupled resonance modes in nanoplasmonic metamaterials. From numeric and experimental results have emerged four design principles to guide fabrication and implementation of metamaterials in bio-related devices and systems. Resonance intensity and sensitivity are enhanced by surface-to-mass of meta-atoms and lattice constant. Fano resonant coupling is dependent on meta-atom polarizability and lattice geometry. Internal reflection in plasmonic metaatom- containing polymer films enhances dissipation rate. Dimensions of self-assembled meta-atoms depend on balancing electrochemical and surface forces. Examples of these principles from our lab compare computation with images and spectra from ordered metal-ceramic and polymeric nanocomposite metamaterials for bio/opto theranostic applications. These principles speed design and description of new architectures for nanoplasmonic metamaterials that show promise for bioapplications.