Edward E. Remsen

Simultaneous absolute determination of particle size and effective density of submicron colloids by disc centrifuge photosedimentometry.

Disc centrifuge photosedimentometry (DCP) with fluids of different densities is used to simultaneously determine the particle size and effective density of spherical silica particles. Incorporation of a calibrated infrared pyrometer into a DCP instrument is shown to enhance the measurement capability of the DCP technique by correcting for the temperature dependence of the spin fluids density and viscosity. Advantages of absolute DCP determinations for size and density analysis relative to standardized DCP measurements include the elimination of instrument standardization with a particle of known density and measurements or estimation of the effective particle density. The reliability of diameter determinations provided by absolute DCP was confirmed using silica particles with nominal diameters ranging from 250 to 700 nm by comparison of these analyses with a diameter determination by transmission electron microscopy for silica particle size standards. Effective densities determined by absolute DCP for the silica particles ranged from 2.02 to 2.34 g/cm(3). These findings indicate that the silica particles have little or no porosity. The reported characterization of colloidal silica using absolute DCP suggests applicability of the technique to a variety of particle types including colloidal materials other than silica, core-shell particles, compositionally heterogeneous mixtures of nanoparticles, and irregularly shaped, structured colloids.

Reduction of artifacts in fluorescence correlation spectroscopy due to sample adsorption on optical glass surfaces.

The preparation of glass cell surfaces that are chemically functionalized with poly(ethylene glycol) (PEG) chains to reduce sample adsorption and their use in fluorescence correlation spectroscopy (FCS) is described. Optical glass coverslips were acid etched and reacted with either 750 Mr PEG (PEG-750) or 5000 Mr PEG (PEG-5000) to produce adsorption-resistant optical surfaces. FCS data for Nile red-loaded Triton X-100 micelles (NR-TX-100) and Alexa Fluor 555-labeled proteins, bovine serum albumin (BSA-A555), lipidized BSA (lipid-BSA-A555), and three low molecular weight dyes deposited on PEGylated coverslips were evaluated. Measurement artifacts due to sample adsorption on the PEG-5000 functionalized coverslips were reduced significantly for the majority of test materials. Calculations of translational diffusion coefficients and Stokes radii confirmed the effectiveness of this approach. PEG-5000 functionalized coverslips were demonstrated as more effective in inhibiting adsorption than PEG-750 functionalized coverslips. Neither of the functionalized coverslips inhibited the adsorption of one test compound, rhodamine B, a dye that adsorbs strongly on glass surfaces. The use of longer PEG chains in conjunction with chemical cross-linking is proposed for producing a denser, less porous PEG layer for the prevention of strongly glass-adsorbing fluorophores that do not interact with the PEG layer.

Analysis of carbohydrates in Fusarium verticillioides using size-exclusion HPLC – DRI and direct analysis in real time ionization – time-of-flight – mass spectrometry (DART-MS)

Direct analysis in real time ionization – time-of-flight – mass spectrometry (DART-MS) and size-exclusion HPLC – DRI are used, respectively, to qualitatively and quantitatively determine the carbohydrates extracted from the corn rot fungus Fusarium verticillioides. In situ permethylation in the DART beam forms tri-methylammonium adducts of the carbohydrates, which enables positive ion MS detection and analysis of these compounds in either whole fungal extracts or size-exclusion separated HPLC fractions of the extracts. This method detects the disaccharide trehalose at concentrations greater than 3.0 ppm. Additionally, this procedure allows for analysis of glucose as well as the sugar alcohols mannitol, arabitol, and glycerol. The reliability of the DART-MS method is confirmed by the absence of trehalose in a mutant strain of F. verticillioides lacking the gene for trehalose-6-phosphate synthase. The capabilities demonstrated here suggest that the DART-MS method, in conjunction with size-exclusion HPLC, is an effective approach for the analysis of saccharide biomarkers in fungi.

Advances in the Characterization of Particle Size Distributions of Abrasive Particles used in CMP

The use of density gradient stabilized centrifugal sedimentation (disc centrifugation) for the characterization of abrasive particles in CMP slurries is reported. For slurries prepared with ceria and colloidal silica abrasives, the technique is demonstrated as capable of providing highly repeatable analyses of the abrasives apparent particle size distribution (PSD). The addition of water soluble organic additives to the slurries is shown to produce large shifts in the apparent PSD relative to the PSD of the pure abrasive particles. Particle-additive interactions driving the shift in apparent PSD could not be interpreted with confidence due to the lack of accurate densities for particle-abrasive complexes formed in the slurry. To address this problem, sucrose density gradients prepared using H2O and D2O were tested as spin fluids of different densities to analyze a colloidal silica standard with a narrow PSD. Preliminary results comparing experimental disc centrifuge data with theoretical simulations of the disc sedimentation pattern suggest that this technique can potentially characterize both the particle diameter and density of abrasive particles in a CMP slurry.

New Particle Metrology for CMP Slurries

A new particle sizing and counting method based on the coupling of flow field-flow fractionation (FFF) with dual-sensor, single particle optical sensing (SPOS) detection is reported. The integration of FFF and SPOS systems was accomplished by means of a dilution interface that preserved the resolution of FFF-separated particles. Analysis of a model mixture of polystyrene latex standards of different diameters established that the FFF-SPOS system can resolve particles into discrete peaks for subsequent particle counting. Application of this method for the analysis of a colloidal silica standard demonstrated its use for materials commonly employed as CMP abrasives. Further development and refinement of the technique will enable compositional and structural analyses of heterogeneous large particle populations constituting commercial CMP slurries.

Ionization Mechanism of Positive-Ion Nitrogen Direct Analysis in Real Time

AbstractNitrogen can be an inexpensive alternative to helium used by direct analysis in real time (DART), especially in consideration of the looming helium shortage. Therefore, the ionization mechanism of positive-ion N2 DART has been systematically investigated. Our experiments suggest that a range of metastable nitrogen species with a variety of internal energies existed and all of them were less energetic than metastable helium atoms. However, compounds with ionization energies (IE) equal to or lower than 10.2 eV (all organic compounds except the extremely small ones) can be efficiently ionized. Because N2 DART was unable to efficiently ionize ambient moisture and common organic solvents such as methanol and acetonitrile, the most important ionization mechanism was direct Penning ionization followed by self-protonation of polar compounds generating [M+H]+ ions. On the other hand, N2 DART was able to efficiently ionize ammonia, which was beneficial in the ionization of hydrogen-bonding compounds with proton affinities (PA) weaker than ammonia generating [M+NH4]+ ions and large PAHs generating [M+H]+ ions through proton transfer. N2 DART was also able to efficiently ionize NO, which led to the ionization of nonpolar compounds such as alkanes and small aromatics generating [M–(2m+1)H]+ (m=0,1…) ions. Lastly, metastable nitrogen species was also able to produce oxygen atoms, which resulted in increased oxygen adducts as the polarity of organic compounds decreased. In comparison with He DART, N2 DART was approximately one order of magnitude less sensitive in generating [M+H]+ ions, but could be more sensitive in generating [M+NH4]+ ions. Graphical Abstractᅟ

Infrared Spectroscopic Analysis of the Adsorption of Pyridine Carboxylic Acids on Colloidal Ceria

Surface adsorption of a homologous series of pyridine carboxylic acids on a hydrated colloidal cerium dioxide (ceria) film is characterized using the combination of experimental and computationally determined infrared (IR) spectra. Experimental analyses employ attenuated total reflectance (ATR) IR spectroscopy of deposited colloidal ceria thin films equilibrated with three pyridine carboxylic acids at pH 3.0, 5.5, and 8.5. The corresponding computational IR spectra for the energy-minimized intermediate and base forms of the pyridine carboxylic acids use density functional theory calculations at the B3LYP/6-311++G** level of theory. Solvent effects are modeled using both the COSMO implicit solvation model and the inclusion of explicit water molecules. Experimental IR spectra show that the adsorptive interactions between the pyridine carboxylic acids and ceria surface are due to the outer-sphere coordination of cerium ions in the films. Vibrational assignments based on combined experimental and computational results indicate that both pyridyl ring nitrogen and carboxylate functional groups account for the interaction of pyridine carboxylic acids at ceria surfaces. Experimentally determined Langmuir constants point to the intermediate form of picolinic acid (pyridine-2-carboxylic acid) as having the strongest adsorption to ceria compared to the other pyridine carboxylic acids investigated. The enhanced adsorption of picolinic acid is attributed to the adjacency of the protonated pyridyl nitrogen and the carboxylate group relative to nicotinic acid (pyridine-3-carboxylic acid) and isonicotinic acid (pyridine-4-carboxylic acid).