Microscopy Publications

2008

Krzyminski KJ, M Jasionowski, and A Gutowska. 2008. "Reversible Sol-Gel Transitions in Aqueous Solutions of N-Isopropylacrylamide Ionic Copolymers ." Polymer International 57(4):592-604. Abstract Ionic copolymers of N-isopropylacrylamide (NIPA) exhibiting sol-gel transitions in aqueous solutions were investigated. The studies were aimed at understanding of the structure-property relationship in design of injectable, in situ forming gels for potential biomedical applications in delivery of therapeutics and tissue engineering. Aqueous solutions of NIPA ionic copolymers were found to flow freely at ambient temperatures and formed soft gels with controlled syneresis above 32°C, the lower critical solution temperature of NIPA. The sol-gel transitions and temperature dependent properties of the resulting gels were analyzed using dynamic rheometry, UV and IR spectrometry, and were found to be controlled by the molecular weight and composition of copolymers, ionization state of comonomers, and composition of aqueous solvent.
Bylaska EJ, M Dupuis, and PG Tratnyek. 2008. "One-Electron-Transfer Reactions of Polychlorinated Ethylenes: Concerted and Stepwise Cleavages." Journal of Physical Chemistry A 112(16):3712-3721. Abstract Reaction barriers were calculated by using ab initio electronic structure methods for the reductive dechlorination of the polychlorinated ethylenes: C2CL4, C2Cl4, C2HCl3, trans-1,2-C2H2Cl2, cis-1,2-C2H2Cl2, 1,1-C2H2Cl2, and C2HCl3. Concerted and stepwise cleavages of R-Cl bonds were considered. Stepwise cleavages yielded lower activation barriers than concerted cleavages for the reduction of C2Cl4, C2HCl3, and trans-1,2-C2H2Cl2 via strong reducing agents. However, for typical ranges of reducing strength concerted cleavages were found to be favored. Both gas-phase and aqueous-phase calculations predicted C2Cl4 to have the lowest reaction barrier. Additionally, the reduction of C2HCl3 was predicted to have a significant amount of selectivity of cis-1,2-C2HCl2 over the corresponding reactions leading to the trans-1,2-C2HCl2, and 1,1-C2HCl2 radicals. These results illustrate how ab initio electronic structure methods, by providing experimentally inaccessible thermodynamics properties and activation energies, are able to sort out possible reactions mechanisms of reactions that have broad relevance in environmental chemistry.
Shin Y, GA Baker, LQ Wang, and GJ Exarhos. 2008. "Investigation of the hygroscopic growth of self-assembled layers of N-alkyl-N-methylpyrrolidinium bromides at the interface between air and organic salt ." Colloids and Surfaces. A, Physicochemical and Engineering Aspects 318(1-3):254-258. doi:10.1016/j.colsurfa.2007.12.045 Abstract We report on the hygroscopic growth of self-assembled lamellae, composed of N-alkyl-N-methylpyrrolidinium bromide (CnMPB; n = 10, 12, 14, 16, 18) surfactant molecules, spontaneously formed at the interface between ambient air and the low-melting organic salt tetrabutylammonium acetate (TBAAc). The organization process to form well-defined hygroscopic bilayer patterns at the air/TBAAc interface was investigated using a combination of time-dependent X-ray diffraction (XRD) and carbon-13 cross-polarization magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR) spectroscopy. CnMPB surfactants containing the highest alkyl chain lengths studied (n = 16, 18) formed highly ordered, fully-interdigitated bilayer patterns with an all-trans conformation of interior methylene carbons. In contrast, CnMPB surfactants with shorter alkane chains (n = 10, 12, 14) in this series formed less-ordered bilayer arrangements with mixed trans/gauche aliphatic character. The lamellar patterns became increasingly ordered with longer exposure to humid air at the air/salt interface.
Lower BH, RD Lins, ZW Oestreicher, TP Straatsma, MF Hochella Jr., L Shi, and SK Lower. 2008. "In Vitro Evolution of a Peptide with a Hematite Binding Motif That May Constitute a Natural Metal-Oxide Binding Archetype." Environmental Science & Technology 42(10):3821-3827. doi:10.1021/es702688c Abstract Phage-display technology was used to evolve peptides that selectively bind to the metal-oxide hematite (Fe2O3) from a library of approximately 3 billion different polypeptides. The sequences of these peptides contained the highly conserved amino acid motif, Ser/Thr-hydrophobic/aromatic-Ser/Thr-Pro-Ser/Thr. To better understand the nature of the peptide−metal oxide binding demonstrated by these experiments, molecular dynamics simulations were carried out for Ser-Pro-Ser at a hematite surface. These simulations show that hydrogen bonding occurs between the two serine amino acids and the hydroxylated hematite surface and that the presence of proline between the hydroxide residues restricts the peptide flexibility, thereby inducing a structural-binding motif. A search of published sequence data revealed that the binding motif (Ser/Thr-Pro-Ser/Thr) is adjacent to the terminal heme-binding domain of both OmcA and MtrC, which are outer membrane cytochromes from the metal-reducing bacterium Shewanella oneidensis MR-1. The entire five amino acid consensus sequence (Ser/Thr-hydrophobic/aromatic-Ser/Thr-Pro-Ser/Thr) was also found as multiple copies in the primary sequences of metal-oxide binding proteins Sil1 and Sil2 from Thalassiosira pseudonana. We suggest that this motif constitutes a natural metal-oxide binding archetype that could be exploited in enzyme-based biofuel cell design and approaches to synthesize tailored metal-oxide nanostructures.
Gardner JS, E Shurdha, CM Wang, LD Lau, RG Rodriguez, and JJ Pak. 2008. "Rapid Synthesis and Size Control of CuInS2 Semi-Conductor Nanoparticles Using Microwave Irradiation." Journal of Nanoparticle Research 10(4):633-641. doi:10.1007/s11051-007-9294-7 Abstract The properties of CuInS2 semi-conductor nanoparticles make them attractive materials for use in next-generation photovoltaics. We have prepared CuInS2 nanoparticles from single source precursors via microwave irradiation. Microwave irradiation methods have allowed us to increase the efficiency of preparation of these materials by providing uniform heating and rapid reaction times. We have also controlled nanoparticle growth in the 3 to 5 nm size range by varying thiolated capping ligand concentrations as well as reaction temperatures and times. Investigation of the photophysical properties of the colloidal nanoparticles were performed using electronic absorption and luminescence emission spectroscopy. Qualitative nanoparticles sizes were determined from the photoluminescence (PLE) data and compared to HRTEM images.
Wu H, J Wang, Z Wang, DR Fisher, and Y Lin. 2008. "Apoferritin-Templated Yttrium Phosphate Nanoparticle Conjugates for Radioimmunotherapy of Cancers." Journal of Nanoscience and Nanotechnology 8(5):2316-2322. doi:10.1166/jnn.2008.177 Abstract We report a templated-synthetic approach based on apoferritin to prepare radionuclide nanoparticle (NP) conjugates. Non-radioactive yttrium (89Y) was used as model target and surrogate for radioyttrium (90Y) to prepare the nanoparticle conjugate. The center cavity and multiple channel structure of apoferritin offer a fast and facile method to precipitate yttrium phosphate by diffusing yttrium and phosphate ions into the cavity of apofrritin, resulting a core-shell nanocomposite. The yttrium phosphate/apoferritin nanoparticle was functionalized with biotin for further application. The synthesized nanoparticle was characterized by transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS). We found that the resulting nanoparticles were uniform in size, with a diameter of around 8 nm. We tested the pre-targeting capability of the biotin-modified yttrium phosphate/apoferritin nanoparticle (yttrium phosphate/apoferritin nanoparticle) conjugate with streptavidin-modified magnetic beads and with aid of biotin-modified fluorecein isothiocyanate (FITC) tracer. This work shows that an yttrium phosphate NP conjugate provides a fast, simple and efficient method to prepare radioactive yttrium conjugate for applications in radioimmunotherapy of cancer.
Wang J, G Liu, H Wu, and Y Lin. 2008. "Sensitive electrochemical immunoassay for 2,4,6-trinitrotoluene based on functionalized silica nanoparticle labels." Analytica Chimica Acta 610(1):112-118. doi:10.1016/j.aca.2008.01.024 Abstract We present a poly(guanine)-functionalized silica nanoparticle (NP) label-based electrochemical immunoassay for sensitively detecting 2,4,6-trinitrotoluene (TNT). This immunoassay takes advantage of magnetic bead–based platform for competitive displacement immunoreactions and separation, and use electroactive nanoparticles as labels for signal amplification. For this assay, anti-TNT-coated magnetic beads interacted with TNT analog-conjugated poly(guanine)-silica NPs and formed analog-anti-TNT immunocomplexes on magnetic beads. The immunocomplexes coated magnetic beads were exposed to TNT samples, which resulted in displacing the analog conjugated poly(guanine) silica NPs into solution by TNT. In contrast, there are no guanine residues releasing into the solution in the absence of TNT. The reaction solution was then separated from the magnetic beads and transferred to the electrode surface for electrochemical measurements of guanine oxidation with Ru(bpy)32+ as mediator. The sensitivity of this TNT assay was greatly enhanced through dual signal amplifications: 1) a large amount of guanine residues on silica nanoparticles is introduced into the test solution by displacement immunoreactions and 2) a Ru(bpy)32+-induced guanine catalytic oxidation further enhances the electrochemical signal. Some experimental parameters for the nanoparticle label-based electrochemical immunoassay were studied and the performance of this assay was evaluated. The method is found to be very sensitive and the detection limit of this assay is ~ 0.1 ng mL-1 TNT. The electrochemical immunoassay based on the poly[guanine]-functionalized silica NP label offers a new approach for sensitive detection of explosives.
Lins RD, ER Vorpagel, M Guglielmi, and TP Straatsma. 2008. "Computer Simulation of Uranyl Uptake by the Rough Lipopolysaccharide Membrane of Pseudomonas aeruginosa." Biomacromolecules 9(1):29-35. doi:10.1021/bm700609r Abstract Heavy metal environmental contaminants cannot be destroyed but require containment, preferably in concentrated form, in a solid or immobile form for recycling or final disposal. Microorganisms are able to take up and deposit high levels of contaminant metals, including radioactive metals such as uranium and plutonium, into their cell wall. Consequently, these microbial systems are of great interest as the basis for potential environmental bioremediation technologies. The outer membranes of Gram-negative microbes are highly non-symmetric and exhibit a significant electrostatic potential gradient across the membrane. This gradient has a significant effect on the uptake and transport of charged and dipolar compounds. However, the effectiveness of microbial systems for environmental remediation will depend strongly on specific properties that determine the uptake of targeted contaminants by a particular cell wall. To aid in the design of microbial remediation technologies, knowledge of the factors that determine the affinity of a particular bacterial outer membrane for the most common ionic species found in contaminated soils and groundwater is of great importance. Using our previously developed model for the lipopolisaccharide (LPS) membrane of Pseudomonas aeruginosa, this work presents the potentials of mean force as the estimate of the free energy profile for uptake of sodium, calcium, chloride, uranyl ions and a water molecule by the bacterial LPS membrane. A compatible classical parameter set for uranyl has been developed and validated. Results show that the uptake of uranyl is energetically a favorable process relative to the other ions studied. At neutral pH, this nuclide is shown to be retained on the surface of the LPS membrane through chelation with the carboxyl and hydroxyl groups located in the outer-core.
Cwiertny DM, J Baltrusaitis, GJ Hunter, A Laskin, M Scherer, and VH Grassian. 2008. "Characterization and Acid-Mobilization Study of Iron-Containing Mineral Dust Source Materials." Journal of Geophysical Research. D. (Atmospheres) 113(D5):Art. No. D05202. doi:10.1029/2007JD009332 Abstract Processes that solubilize the iron in mineral dust aerosols may increase the amount of iron supplied to ocean surface waters, and thereby stimulate phytoplankton productivity. It was recently proposed that mixing of mineral dusts with SO2 and HNO3 produces extremely acidic environments that favor the formation of bioavailable Fe(II). Here, four authentic mineral dust source materials (Saudi Beach sand (SB), Inland Saudi sand (IS), Saharan Sand (SS) and China Loess (CL)) and one commercial reference material (Arizona Test Dust (AZTD)) were spectroscopically characterized, and their dissolution at pH 1 was examined in aqueous batch systems. Spectroscopic analyses indicated that the bulk and near-surface region of all samples possessed similar elemental compositions and that iron was unevenly distributed among dust 10 particles. Mössbauer spectroscopy revealed Fe(III) in all samples, although SB, CL and AZTD also contained appreciable Fe(II). Both Fe(II) and Fe(III) were primarily substituted into aluminosilicates, although CL, AZTD and IS also contained Fe(III) oxides. Total iron solubility (defined as the summed concentration of dissolved Fe(II) and Fe(III) measured after 24 h) ranged 14 between 4-12% of the source materials’ iron content, but did not scale with either the surface area or the iron content of the samples. This suggests that other factors such as iron speciation and mineralogy may play a key role in iron solubility. Also, the elevated nitrate concentrations encountered from nitric acid at pH 1 suppressed dissolution of Fe(II) from AZTD, CL and SB particles, which we propose results from the surface-mediated, non-photochemical reduction of nitrate by Fe(II).
Grate JW, OB Egorov, MJ O'Hara, and TA Devol. 2008. "Radionuclide Sensors for Environmental Monitoring: From Flow Injection Solid-Phase Absorptiometry to Equilibration-Based Preconcentrating Minicolumn Sensors with Radiometric Detection." Chemical Reviews 108(2):543-562. doi:10.1021/cr068115u Abstract The development of in situ sensors for ultratrace detection applications in process control and environmental monitoring remains a significant challenge. Such sensors must meet difficult detection limit requirements while selectively detecting the analyte of interest in complex or otherwise challenging sample matrixes. Nowhere are these requirements more daunting than in the field of radionuclide sensing. The detection limit requirements can be extremely low. Nevertheless, a promising approach to radionuclide sensing based on preconcentrating minicolumn sensors has been developed. In addition, a method of operating such sensors, which we call equilibration-based sensing, has been developed that provides substantial preconcentration and a signal that is proportional to analyte concentration, while eliminating the need for reagents to regenerate the sorbent medium following each measurement. While this equilibration-based sensing method was developed for radionuclide sensing, it can be applied to nonradioactive species as well, given a suitable on-column detection system. By replacing costly sampling and laboratory analysis procedures, in situ sensors could have a significant impact on monitoring and long term stewardship applications. The aim of this review is to cover radionuclide sensors that combine some form of selective sorption with a radiometric detection method, andas a primary aimto comprehensively review preconcentrating minicolumn sensors for radionuclide detection. As a secondary aim, we will cover radionuclide sensors that combine sorption and scintillation in formats other than minicolumn sensors. We are particularly concerned with the detection of alpha- and beta-emitting radionuclides, which present particular challenges for measurements in liquid media.

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