Interfacial and Confined Colloidal Rod Diffusion.

Optical microscopy is used to measure translational and rotational diffusion of colloidal rods near a single wall, confined between parallel walls, and within quasi-2D porous media as a function of rod aspect ratio and aqueous solution ionic strength. Translational and rotational diffusivities are obtained as rod particles experience positions closer to boundaries and for larger aspect ratios. Models based on position dependent hydrodynamic interactions quantitatively capture diffusivities in all geometries and indicate particle-wall separations in agreement with independent estimates based on electrostatic interactions. Short-time translational diffusion in quasi-2D porous media is insensitive to porous media area fraction, which appears to arise from a balance of hydrodynamic hindrance and enhanced translation due to parallel alignment along surfaces. Findings in this work provide a basis to interpret and predict interfacial and confined colloidal rod transport relevant to biological, environmental, and synthetic material systems.

Anomalous silica colloid stability and gel layer mediated interactions.

Total internal reflection microscopy (TIRM) is used to measure SiO2 colloid ensembles over a glass microscope slide to simultaneously obtain interactions and stability as a function of pH (4-10) and NaCl concentration (0.1-100 mM). Analysis of SiO2 colloid Brownian height excursions yields kT-scale potential energy vs separation profiles, U(h), and diffusivity vs separation profiles, D(h), and determines whether particles are levitated or irreversibly deposited (i.e., stable). By including an impermeable SiO2 "gel layer" when fitting van der Waals, electrostatic, and steric potentials to measured net potentials, gel layers are estimated to be ~10 nm thick and display an ionic strength collapse. The D(h) results indicate consistent surface separation scales for potential energy profiles and hydrodynamic interactions. Our measurements and model indicate how SiO2 gel layers influence van der Waals (e.g., dielectric properties), electrostatics (e.g., shear plane), and steric (e.g., layer thickness) potentials to understand the anomalous high ionic strength and high pH stability of SiO2 colloids.

Transport of oxidized multi-walled carbon nanotubes through silica based porous media: influences of aquatic chemistry, surface chemistry, and natural organic matter.

This paper provides results from studies of the transport of oxidized multi-walled carbon nanotubes (O-MWCNTs) of varying surface oxygen concentrations under a range of aquatic conditions and through uniform silica glass bead media. In the presence of Na(+), the required ionic strength (IS) for maximum particle attachment efficiency (i.e., the critical deposition concentration, or CDC) increased as the surface oxygen concentration of the O-MWCNTs or pH increased, following qualitative tenets of theories based on electrostatic interactions. In the presence of Ca(2+), CDC values were lower than those with Na(+) present, but were no longer sensitive to surface oxygen content, suggesting that Ca(2+) impacts the interactions between O-MWCNTs and glass beads by mechanisms other than electrostatic alone. The presence of Suwannee River natural organic matter (SRNOM) decreased the attachment efficiency of O-MWCNTs in the presence of either Na(+) or Ca(2+), but with more pronounced effects when Na(+) was present. Nevertheless, low concentrations of SRNOM (<4 mg/L of dissolved organic carbon) were sufficient to mobilize all O-MWCNTs studied at CaCl2 concentrations as high as 10 mM. Overall, this study reveals that NOM content, pH, and cation type show more importance than surface chemistry in affecting O-MWCNTs deposition during transport through silica-based porous media.

Influence of surface oxygen on the interactions of carbon nanotubes with natural organic matter.

The sorption properties of natural organic matter (NOM) with oxidized multiwalled carbon nanotubes (O-MWCNTs) in simple electrolytes has been studied, as well as the effect that NOM concentration, pH, and O-MWCNT surface chemistry have on CNT stability under environmentally relevant conditions. As O-MWCNT oxygen content increased, NOM sorption decreased in simple electrolytes for a common set of solution conditions. For each O-MWCNT, NOM sorption increased with increasing ionic strength and decreasing pH, although the sensitivity of NOM sorption to these water quality parameters increased as the O-MWCNT oxygen content increased. Collectively, these observations indicate that NOM sorption by O-MWCNTs is determined by favorable hydrophobic π-π interactions that are moderated by repulsive electrostatic forces between negatively charged carboxylic acid functional groups on the O-MWCNTs and NOM. Stability studies conducted in artificial groundwater revealed that CNT stability is influenced by both the NOM concentration and pH, but stability was largely independent of the O-MWCNT oxygen concentration. These findings contrast with the marked effect that surface oxygen has on CNT stability in simple electrolytes. Electrophoretic mobility measurements revealed that the stabilizing effects of adsorbed NOM are due to the introduction of steric repulsion between NOM-coated CNTs, rather than from changes to surface charge.

Chemical and structural characterization of carbon nanotube surfaces.

To utilize carbon nanotubes (CNTs) in various commercial and scientific applications, the graphene sheets that comprise CNT surfaces are often modified to tailor properties, such as dispersion. In this article, we provide a critical review of the techniques used to explore the chemical and structural characteristics of CNTs modified by covalent surface modification strategies that involve the direct incorporation of specific elements and inorganic or organic functional groups into the graphene sidewalls. Using examples from the literature, we discuss not only the popular techniques such as TEM, XPS, IR, and Raman spectroscopy but also more specialized techniques such as chemical derivatization, Boehm titrations, EELS, NEXAFS, TPD, and TGA. The chemical or structural information provided by each technique discussed, as well as their strengths and limitations. Particular emphasis is placed on XPS and the application of chemical derivatization in conjunction with XPS to quantify functional groups on CNT surfaces in situations where spectral deconvolution of XPS lineshapes is ambiguous.

The persistence of illicit drug smoke residues and their recovery from common household surfaces.

Third-hand smoke is the residue remaining on surfaces during smoking events. It is composed of particles and vapours that form upon heating. The phrase 'third-hand smoke' is primarily used to describe nicotine and other chemicals from cigarettes, but any residues formed from the smoking of various substances could be classified similarly. There has been an increasing body of research on third-hand smoke from cigarettes in the last decade, but little has been done in regards to understanding the persistence of particles and vapours from illicit drugs. In this work, small samples of cocaine and methamphetamine were volatilized to produce an illicit drug smoke that was collected onto various surface materials and left exposed to ambient conditions over 672 h (four weeks). Chemical analyses by electrospray ionization-mass spectrometry of residues on silicon, plastic, laminate, and artificial leather surfaces indicated a rapid decrease in recovery of the parent molecule, with varied formation of decomposition products over the first 168 h of exposure. Measurable amounts of the parent molecule were still present after 672 h, exhibiting a strong persistence of these drugs on various household materials. This is important in a forensic science context, as third-hand smoke residues could provide a viable source of trace evidence previously not utilized. Published 2016. This article is a U.S. Government work and is in the public domain in the USA.

Photofading in cotton fibers dyed using red, yellow, and blue direct dyes during examination with microspectrophotometry (MSP).

Microspectrophotometry (MSP) is a rapid, nondestructive technique for the analysis of color in textile fibers. This technique combines microscopy and ultraviolet (UV)/visible (Vis) spectroscopy, allowing for very small colored samples, like dyed textile fibers, to be analyzed directly and thereby eliminates the need for time consuming and destructive extractions. While MSP is generally accepted to be a nondestructive evaluation method, a loss of color during analysis, or photofading can occur. In this work, cotton fabric dyed with blue, yellow, and red direct dyes at different concentrations. Dye photofading during MSP examination was investigated by measuring the absorbance at a specific position on the fibers from these fabrics, periodically over the course of 30 minutes. Visible color loss and a reduction in absorbance was observed for all three colors, but was most pronounced for the fibers dyed red. A major goal of this study is to increase awareness of the photofading phenomenon when analyzing cotton fibers using MSP.

Analysis of oligomeric peroxides in synthetic triacetone triperoxide samples by tandem mass spectrometry.

Oligomeric peroxides formed in the synthesis of triacetone triperoxide (TATP) have been analyzed by mass spectrometry utilizing both electrospray ionization (ESI) and chemical ionization (CI) to form sodiated adducts (by ESI) and ammonium adducts (by CI and ESI). Tandem mass spectrometry and deuterium isotopic labeling experiments have been used to elucidate the collision-induced dissociation (CID) mechanisms for the adducts. The CID mechanisms differ for the sodium and ammonium adducts and vary with the size of the oligoperoxide. The sodium adducts of the oligoperoxides, H[OOC(CH(3))(2)](n)OOH, do not cyclize under CID, whereas the ammonium adducts of the smaller oligoperoides (n < 6) do form the cyclic peroxides under CID. Larger oligoperoxide adducts with both sodium and ammonium undergo dissociation through cleavage of the backbone under CID to form acyl- and hydroperoxy-terminated oligomers of the general form CH(3)C(O)[OOC(CH(3))(2)](x)OOH, where x is an integer less than the original oligoperoxide degree of oligomerization. The oligoperoxide distribution is shown to vary batch-to-batch in the synthesis of TATP and the post-blast distribution differs slightly from the distribution in the uninitiated material. The oligoperoxides are shown to be decomposed under gentle heating.