Design and synthesis of plasmonic magnetic nanoparticles

Core–shell nanoparticles containing both iron oxide and gold are proposed for bioseparation applications. The surface plasmon resonance of gold makes it possible to track the positions of individual particles, even when they are smaller than the optical diffraction limit. The synthesis of water-dispersible iron oxide-gold nanoparticles is described. Absorption spectra show the plasmon peaks for Au shells on silica particles, suggesting that thin shells may be sufficient to impart a strong surface plasmon resonance to iron oxide-gold nanoparticles. Dark field optical microscopy illustrates the feasibility of single-particle detection. Calculations of magnetophoretic and drag forces for particles of different sizes reveal design requirements for effective separation of these small particles.     

Measurement of Catalytic Reaction Kinetics for Adsorbed Enzyme Monolayers

We present a new assay based on total internal reflection fluorescence (TIRF) to quantify the catalytic activity of adsorbed enzyme monolayers on macroscopically flat surfaces. The need for such an assay derives from a general shortage of assay methods that are sufficiently sensitive to measure reaction kinetics for just a single monolayer of enzymes. The assay is based on the enzymatic conversion of a soluble, nonfluorescent fluorogenic substrate reagent to a soluble, highly fluorescent product. The reaction occurs at the solid-liquid interface where the enzymes are adsorbed. Fluorogenic substrates are introduced to the adsorbed layer by convective diffusion from solutions undergoing steady laminar slit flow. The exponentially decaying evanescent wave that is produced by total internal reflection serves as a "spectroscopic ruler" to resolve the spatial concentration profile of fluorescent products in solution near the interface. By measuring the steady-state fluorescence signal as a function of the Peclet number that characterizes mass transfer conditions in the experiment, it is possible to determine the enzymatic reaction rate. Here we present the development of the method and its application to a test system of beta-galactosidase adsorbed to methylated silica surfaces. Compared to the enzymatic rate constants for this enzyme in free solution, adsorption decreased the Michaelis-Menten rate constant kcat by a factor of 10 and increased the equilibrium binding constant Km by a factor of 4.5. Thus the intrinsic activity of the enzyme, as represented by the ratio kcat/Km, decreased 45-fold due to adsorption. Copyright 1999 Academic Press.     

Simultaneous determination of multiple platycosides with a single reference standard in Platycodi Radix by high‐performance liquid chromatography coupled with evaporative light scattering detection

A traditional external standard method using HPLC coupled with evaporative light scattering detection has been developed for fast and accurate determination of seven platycosides in Platycodi Radix. However, inevitable difficulties in reference standards preparation process, which are quite costly and time consuming, have made its application limited. To avoid this inconvenience, a simultaneous determination of multiple components with a single reference standard strategy, which could be realized by calibrating the standard curve with internal standard and response factors, was introduced to the HPLC coupled with evaporative light scattering detection method. This is the first time that an incorporation of these two methods has been realized. Among seven ingredients, platycodin D was selected as the internal standard for its relatively easy preparation and low cost. Moreover, according to the investigation on concentration‐dependent effects over response factors and robustness test, platycoside E, deapioplatycodin D, platycodin D, and polygalacin D₂ were chosen to be the indicators for this novel method. The present method has not shown statistically significant differences with a traditional external standard method as verified sample analysis by the F‐test (p = 95%, n = 6).     

Liquid chromatography/mass spectrometry analysis of PHY906, a Chinese medicine formulation for cancer therapy

PHY906 is a Chinese medicine formulation prepared from four medicinal herbs for adjuvant cancer chemotherapy. In this paper, liquid chromatography/electrospray ionization time-of-flight mass spectrometry (LC/ESI-TOFMS) was used to clarify the chemical composition of PHY906. The aqueous extract of PHY906 was separated on a Waters Atlantis C(18) column, and was eluted with acetonitrile/0.05% (v/v) formic acid. The separated compounds were identified with pure standards, or tentatively characterized by analyzing their mass spectra recorded in both negative and positive ion polarity modes. Further structural information was obtained from in-source fragmentation. Based on the LC/MS analysis, we proposed the structures for 64 bioactive compounds, including flavonoids, triterpene saponins, and monoterpene glycosides. All the compounds identified from PHY906 were further assigned in the four individual herbs, and some of them are reported for the first time.     

Electroosmotically enhanced mass transfer through polyacrylamide gels

We present an internal pumping strategy to enhance solute fluxes in polymer gels. The method is based on electroosmotic flow driven by an electric field applied across a gel that has been doped with charged colloidal inclusions. This work is motivated by the need to enhance the transport in gel-based biosensor devices whose response dynamics are often mass transfer limited. In this case, polyacrylamide gel slabs were doped with immobilized, charged silica colloids, and the flux of a fluorescent tracer was measured as a function of applied field strength, the volume fraction and size of the colloidal silica inclusions, and the bulk electrolyte composition. Significant flux enhancements were achieved with applied electric currents on the order of a few mA. Control experiments indicated that the flux enhancement was not due to any distortion of the gel diffusional properties in response to the presence of the inclusions. At a constant inclusion volume fraction, the electroosmotic solute flux enhancement was strongest for the smallest particle sizes that provide the highest total surface area, consistent with the electroosmotic mechanism whereby fluid flow is generated along the solid/liquid interface.     

The role of electrode impedance and electrode geometry in the design of microelectrode systems

Microelectromechanical systems (MEMS) employing spatially and/or temporally nonuniform electric fields have been extensively employed to control the motion of suspended particles or fluid flow. Design and control of microelectromechanical processes require accurate calculations of the electric field distribution under varying electrolyte conditions. Polarization of electrodes under the application of an oscillating voltage difference produces dynamic electrical double layers. The capacitive nature of the double layers significantly inhibits the penetration of the electric field through the double layer and into the surrounding bulk electrolyte at low frequencies. This paper quantitatively discusses the effect of electrode impedance on the electric field distribution as a function of field frequency, electrolyte composition, and electrode zeta potential in microelectrode systems. The design principles for the electrode geometry and configuration are also discussed in terms of their effects on the electric field magnitude and nonuniformity.     

Stabilization of aqueous nanoscale zerovalent iron dispersions by anionic polyelectrolytes: adsorbed anionic polyelectrolyte layer properties and their effect on aggregation and sedimentation

Nanoscale zerovalent iron (NZVI) particles are 5–40 nm sized Fe⁰/Fe-oxide particles that rapidly transform many environmental contaminants to benign products and are a promising in situ remediation agent. Rapid aggregation and limited mobility in water-saturated porous media limits the ability to deliver NZVI dispersions in the subsurface. This study prepares stable NZVI dispersions through physisorption of commercially available anionic polyelectrolytes, characterizes the adsorbed polymer layer, and correlates the polymer coating properties with the ability to prevent rapid aggregation and sedimentation of NZVI dispersions. Poly(styrene sulfonate) with molecular weights of 70 k and 1,000 k g/mol (PSS70K and PSS1M), carboxymethyl cellulose with molecular weights of 90 k and 700 k g/mol (CMC90K and CMC700K), and polyaspartate with molecular weights of 2.5 k and 10 k g/mol (PAP2.5K and 10K) were compared. Particle size distributions were determined by dynamic light scattering during aggregation. The order of effectiveness to prevent rapid aggregation and stabilize the dispersions was PSS70K(83%) > ≈PAP10K(82%) > PAP2.5K(72%) > CMC700K(52%), where stability is defined operationally as the volume percent of particles that do not aggregate after 1 h. CMC90K and PSS1M could not stabilize RNIP relative to bare RNIP. A similar trend was observed for their ability to prevent sedimentation, with 40, 34, 32, 20, and 5 wt%, of the PSS70K, PAP10K, PAP2.5K, CMC700K, and CMC90K modified NZVI remaining suspended after 7 h of quiescent settling, respectively. The stable fractions with respect to both aggregation and sedimentation correlate well with the adsorbed polyelectrolyte mass and thickness of the adsorbed polyelectrolyte layers as determined by Oshima’s soft particle theory. A fraction of the particles cannot be stabilized by any modifier and rapidly agglomerates to micron sized aggregates, as is also observed for unmodified NZVI. This non-dispersible fraction is attributed to strong magnetic attractions among the larger particles present in the polydisperse NZVI slurry, as the magnetic attractive forces increase as r⁶.     

Calculation of the dynamic impedance of the double layer on a planar electrode by the theory of electrokinetics

Applications of microelectromechanical systems in the biotechnological arena (bioMEMS) are a subject of great current interest. Accurate calculation of electric field distribution in these devices is essential to the understanding and design of processes such as dielectrophoresis and AC electroosmosis that drive MEMS-based devices. In this paper, we present the calculation of the electrical double-layer impedance (Z(el)) of an ideally polarizable plane electrode using the standard model of colloidal electrokinetics. The frequency variation of the electrical potential drop across the double layer above a planar electrode in a general electrolyte solution is discussed as a function of the electrode zeta potential zeta, the Debye length kappa(-1), the electrolyte composition and the bulk region thickness L.     

Direct force measurement of the stability of poly(ethylene glycol)-polyethylenimine graft films

The stability and passivity of poly(ethylene glycol)-polyethylenimine (PEG-PEI) graft films are important for their use as antifouling coatings in a variety of biotechnology applications. We have used AFM colloidal-probe force measurements combined with optical reflectometry to characterize the surface properties and stability of PEI and dense PEG-PEI graft films on silica. Initial contact between bare silica probes and PEI-modified surfaces yields force curves that exhibit a long-range electrostatic repulsion and short-range attraction between the surfaces, indicating spontaneous desorption of PEI in the aqueous medium. Further transfer of PEI molecules to the probe occurs with subsequent application of forces between FR = 300 and 500 microN/m. The presence of PEG reduces the adhesive properties of the PEI surface and prevents transfer of PEI molecules to the probe with continuous contact, though an initial desorption of PEI still occurs. Glutaraldehyde crosslinking of the graft films prevents both the initial desorption and subsequent transfer of the PEI, resulting in sustained attractive interaction forces of electrostatic origin between the negatively charged probe and the positively charged copolymer graft films.     

Surface modification of fluorosilicone acrylate RGP contact lens via low-temperature argon plasma

A fluorosilicone acrylate rigid gas permeable (RGP) contact lens was modified via argon plasma to improve surface hydrophilicity and resistance to protein deposition. The influence of plasma treatment on surface chemical structure, hydrophilicity and morphology of RGP lens was investigated by X-ray photoelectron spectrometer (XPS), contact angle measurements and scanning electron microscope (SEM), respectively. The contact angle results showed that the hydrophilicity of the contact lens was improved after plasma treatment. XPS results indicated that the incorporation of oxygen-containing groups on surface and the transformation of silicone into hydrophilic silicate after plasma treatment are the main reasons for the surface hydrophilicity improvement. SEM results showed that argon plasma with higher power could lead to surface etching.