Search

Search Results

• 1. [Article] The Atmosphere can be a Source of Certain Water Soluble Volatile Organic Compounds in Urban Streams

  Surface water and air volatile organic compound (VOC) data from 10 U. S. Geological Survey monitoring sites were used to evaluate the potential for direct transport of VOCs from the atmosphere to urban ...

  Citation × Citation Citation Abstract Copy Title: The Atmosphere can be a Source of Certain Water Soluble Volatile Organic Compounds in Urban Streams Author: Kenner, Scott J, Bender, David A., Pankow, James F., Zogorski, John S. Year: 2014 Surface water and air volatile organic compound (VOC) data from 10 U. S. Geological Survey monitoring sites were used to evaluate the potential for direct transport of VOCs from the atmosphere to urban streams. Analytical results of 87 VOC compounds were screened by evaluating the occurrence and detection levels in both water and air, and equilibrium concentrations in water (C-w(s)) based on the measured air concentrations. Four compounds (acetone, methyl tertiary butyl ether, toluene, and m- & p-xylene) were detected in more than 20% of water samples, in more than 10% of air samples, and more than 10% of detections in air were greater than long-term method detection levels (LTMDL) in water. Benzene was detected in more than 20% of water samples and in more than 10% of air samples. Two percent of benzene detections in air were greater than one-half the LTMDL in water. Six compounds (chloroform, p-isopropyltoluene, methylene chloride, perchloroethene, 1,1,1-trichloroethane, and trichloroethene) were detected in more than 20% of water samples and in more than 10% of air samples. Five VOCs, toluene, m- & p-xylene, methyl tert-butyl ether (MTBE), acetone, and benzene were identified as having sufficiently high concentrations in the atmosphere to be a source to urban streams. MTBE, acetone, and benzene exhibited behavior that was consistent with equilibrium concentrations in the atmosphere. Title: The Atmosphere can be a Source of Certain Water Soluble Volatile Organic Compounds in Urban Streams Author: Kenner, Scott J, Bender, David A., Pankow, James F., Zogorski, John S. Year: 2014 Surface water and air volatile organic compound (VOC) data from 10 U. S. Geological Survey monitoring sites were used to evaluate the potential for direct transport of VOCs from the atmosphere to urban streams. Analytical results of 87 VOC compounds were screened by evaluating the occurrence and detection levels in both water and air, and equilibrium concentrations in water (C-w(s)) based on the measured air concentrations. Four compounds (acetone, methyl tertiary butyl ether, toluene, and m- & p-xylene) were detected in more than 20% of water samples, in more than 10% of air samples, and more than 10% of detections in air were greater than long-term method detection levels (LTMDL) in water. Benzene was detected in more than 20% of water samples and in more than 10% of air samples. Two percent of benzene detections in air were greater than one-half the LTMDL in water. Six compounds (chloroform, p-isopropyltoluene, methylene chloride, perchloroethene, 1,1,1-trichloroethane, and trichloroethene) were detected in more than 20% of water samples and in more than 10% of air samples. Five VOCs, toluene, m- & p-xylene, methyl tert-butyl ether (MTBE), acetone, and benzene were identified as having sufficiently high concentrations in the atmosphere to be a source to urban streams. MTBE, acetone, and benzene exhibited behavior that was consistent with equilibrium concentrations in the atmosphere. Close

• 2. [Article] A Method to Derivatize Surface Silanol Groups to Si-Alkyl Groups in Carbon-Doped Silicon Oxides

  A carbon-doped silicon oxide (CDO) finds use as a material with a low dielectric constant (k) for copper interconnects in multilayered integrated circuits (ICs). Hydrophilic silanol groups (Si–OH) on its ...

  Citation × Citation Citation Abstract Copy Title: A Method to Derivatize Surface Silanol Groups to Si-Alkyl Groups in Carbon-Doped Silicon Oxides Author: Darmakkolla, Srikar Rao, Tran, Hoang, Gupta, Atul, Rananavare, Shankar B. Year: 2016 A carbon-doped silicon oxide (CDO) finds use as a material with a low dielectric constant (k) for copper interconnects in multilayered integrated circuits (ICs). Hydrophilic silanol groups (Si–OH) on its surface, however, can attract moisture, thereby causing an undesirable increase in the dielectric constant. Modification of the exposed hydrophilic surface to a hydrophobic functional group provides one solution to this problem. We report here a strategy for converting surface Si–OH to hydrophobic silicon hydride (Si–H) without affecting the internal oxide network in CDO. The approach involves esterification of the exposed silanol to its triflate (silyltrifluoromethanesulfonate, Si–O–Tf), followed by reduction to Si–H with diisobutylaluminum hydride. Si–H is further modified by a photochemical reaction with an alkene (1-octadecene) to yield Si–R (R = –C18H37) to provide a more moisture resistant, and less polar Si–C as opposed to the Si–O backbone. Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectrometry (XPS), and measurements of the contact angle with water substantiated the successful conversion. The reaction scheme is versatile, transforming silanol groups to silicon hydride in widely varying chemical sites, from small molecules to the surfaces of silica gels, SiOx and CDO wafers. A comparison with the films (self-assembled monolayers) derivatized with the octadecyltrichlorosilane indicated that the new method leads to a thicker (≈5 nm) but more loosely packed hydrocarbon film with slightly lower contact angles. Title: A Method to Derivatize Surface Silanol Groups to Si-Alkyl Groups in Carbon-Doped Silicon Oxides Author: Darmakkolla, Srikar Rao, Tran, Hoang, Gupta, Atul, Rananavare, Shankar B. Year: 2016 A carbon-doped silicon oxide (CDO) finds use as a material with a low dielectric constant (k) for copper interconnects in multilayered integrated circuits (ICs). Hydrophilic silanol groups (Si–OH) on its surface, however, can attract moisture, thereby causing an undesirable increase in the dielectric constant. Modification of the exposed hydrophilic surface to a hydrophobic functional group provides one solution to this problem. We report here a strategy for converting surface Si–OH to hydrophobic silicon hydride (Si–H) without affecting the internal oxide network in CDO. The approach involves esterification of the exposed silanol to its triflate (silyltrifluoromethanesulfonate, Si–O–Tf), followed by reduction to Si–H with diisobutylaluminum hydride. Si–H is further modified by a photochemical reaction with an alkene (1-octadecene) to yield Si–R (R = –C18H37) to provide a more moisture resistant, and less polar Si–C as opposed to the Si–O backbone. Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectrometry (XPS), and measurements of the contact angle with water substantiated the successful conversion. The reaction scheme is versatile, transforming silanol groups to silicon hydride in widely varying chemical sites, from small molecules to the surfaces of silica gels, SiOx and CDO wafers. A comparison with the films (self-assembled monolayers) derivatized with the octadecyltrichlorosilane indicated that the new method leads to a thicker (≈5 nm) but more loosely packed hydrocarbon film with slightly lower contact angles. Close

• 3. [Article] Hydrophobic Surfactant Proteins Strongly Induce Negative Curvature

  The hydrophobic surfactant proteins SP-B and SP-C greatly accelerate the adsorption of vesicles containing the surfactant lipids to form a film that lowers the surface tension of the air/water interface ...

  Citation × Citation Citation Abstract Copy Title: Hydrophobic Surfactant Proteins Strongly Induce Negative Curvature Author: Chavarha, Mariya, Loney, Ryan W., Rananavare, Shankar B., Hall, Stephen B. Year: 2015 The hydrophobic surfactant proteins SP-B and SP-C greatly accelerate the adsorption of vesicles containing the surfactant lipids to form a film that lowers the surface tension of the air/water interface in the lungs. Pulmonary surfactant enters the interface by a process analogous to the fusion of two vesicles. As with fusion, several factors affect adsorption according to how they alter the curvature of lipid leaflets, suggesting that adsorption proceeds via a rate-limiting structure with negative curvature, in which the hydrophilic face of the phospholipid leaflets is concave. In the studies reported here, we tested whether the surfactant proteins might promote adsorption by inducing lipids to adopt a more negative curvature, closer to the configuration of the hypothetical intermediate. Our experiments used x-ray diffraction to determine how the proteins in their physiological ratio affect the radius of cylindrical monolayers in the negatively curved, inverse hexagonal phase. With binary mixtures of dioleoylphosphatidylethanolamine (DOPE) and dioleoylphosphatidylcholine (DOPC), the proteins produced a dose-related effect on curvature that depended on the phospholipid composition. With DOPE alone, the proteins produced no change. With an increasing mol fraction of DOPC, the response to the proteins increased, reaching a maximum 50% reduction in cylindrical radius at 5% (w/w) protein. This change represented a doubling of curvature at the outer cylindrical surface. The change in spontaneous curvature, defined at approximately the level of the glycerol group, would be greater. Analysis of the results in terms of a Langmuir model for binding to a surface suggests that the effect of the lipids is consistent with a change in the maximum binding capacity. Our findings show that surfactant proteins can promote negative curvature, and support the possibility that they facilitate adsorption by that mechanism. Title: Hydrophobic Surfactant Proteins Strongly Induce Negative Curvature Author: Chavarha, Mariya, Loney, Ryan W., Rananavare, Shankar B., Hall, Stephen B. Year: 2015 The hydrophobic surfactant proteins SP-B and SP-C greatly accelerate the adsorption of vesicles containing the surfactant lipids to form a film that lowers the surface tension of the air/water interface in the lungs. Pulmonary surfactant enters the interface by a process analogous to the fusion of two vesicles. As with fusion, several factors affect adsorption according to how they alter the curvature of lipid leaflets, suggesting that adsorption proceeds via a rate-limiting structure with negative curvature, in which the hydrophilic face of the phospholipid leaflets is concave. In the studies reported here, we tested whether the surfactant proteins might promote adsorption by inducing lipids to adopt a more negative curvature, closer to the configuration of the hypothetical intermediate. Our experiments used x-ray diffraction to determine how the proteins in their physiological ratio affect the radius of cylindrical monolayers in the negatively curved, inverse hexagonal phase. With binary mixtures of dioleoylphosphatidylethanolamine (DOPE) and dioleoylphosphatidylcholine (DOPC), the proteins produced a dose-related effect on curvature that depended on the phospholipid composition. With DOPE alone, the proteins produced no change. With an increasing mol fraction of DOPC, the response to the proteins increased, reaching a maximum 50% reduction in cylindrical radius at 5% (w/w) protein. This change represented a doubling of curvature at the outer cylindrical surface. The change in spontaneous curvature, defined at approximately the level of the glycerol group, would be greater. Analysis of the results in terms of a Langmuir model for binding to a surface suggests that the effect of the lipids is consistent with a change in the maximum binding capacity. Our findings show that surfactant proteins can promote negative curvature, and support the possibility that they facilitate adsorption by that mechanism. Close

• 4. [Article] Aqueous Red-Emitting Silicon Nanoparticles for Cellular Imaging: Consequences of Protecting Against Surface Passivation by Hydroxide and Water for Stable Red Emission

  Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis ...

  Citation × Citation Citation Abstract Copy Title: Aqueous Red-Emitting Silicon Nanoparticles for Cellular Imaging: Consequences of Protecting Against Surface Passivation by Hydroxide and Water for Stable Red Emission Author: Chiu, Sheng-Kuei, Manhat, Beth Ann, DeBenedetti, William J.I., Brown, Anna L., Fichter, Katye, Vu, Tania, Eastman, Micah, Jiao, Jun, Goforth, Andrea Mitchell Year: 2013 Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis and surface modification strategy that protects Si NPs and preserves red photoluminescence (PL) in water for more than 6 mo. The Si NPs were synthesized via high temperature reaction, liberated from an oxide matrix, and functionalized via hydrosilylation to yield hydrophobic particles. The hydrophobic Si NPs were phase transferred to water using the surfactant cetyltrimethylammonium bromide (CTAB) with retention of red PL. CTAB apparently serves a double role in providing stable, aqueous, red-emitting Si NPs by (i) forming a hydrophobic barrier between the Si NPs and water and (ii) providing aqueous colloidal stability via the polar head group. We demonstrate preservation of the aqueous red emission of these Si NPs in biological media and examine the effects of pH on emission color. Title: Aqueous Red-Emitting Silicon Nanoparticles for Cellular Imaging: Consequences of Protecting Against Surface Passivation by Hydroxide and Water for Stable Red Emission Author: Chiu, Sheng-Kuei, Manhat, Beth Ann, DeBenedetti, William J.I., Brown, Anna L., Fichter, Katye, Vu, Tania, Eastman, Micah, Jiao, Jun, Goforth, Andrea Mitchell Year: 2013 Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis and surface modification strategy that protects Si NPs and preserves red photoluminescence (PL) in water for more than 6 mo. The Si NPs were synthesized via high temperature reaction, liberated from an oxide matrix, and functionalized via hydrosilylation to yield hydrophobic particles. The hydrophobic Si NPs were phase transferred to water using the surfactant cetyltrimethylammonium bromide (CTAB) with retention of red PL. CTAB apparently serves a double role in providing stable, aqueous, red-emitting Si NPs by (i) forming a hydrophobic barrier between the Si NPs and water and (ii) providing aqueous colloidal stability via the polar head group. We demonstrate preservation of the aqueous red emission of these Si NPs in biological media and examine the effects of pH on emission color. Close

• 5. [Article] Minimizing Corrosion of Outdoor Metalworks Using Dispersed Chemically Stabilized Nanoclays in Polyvinylidene Fluoride Latex Coatings

  Nanoclays are small enough to appear optically transparent, yet they have large surface-to-volume and high aspect ratios that can significantly inhibit water diffusion when incorporated into protective ...

  Citation × Citation Citation Abstract Copy Title: Minimizing Corrosion of Outdoor Metalworks Using Dispersed Chemically Stabilized Nanoclays in Polyvinylidene Fluoride Latex Coatings Author: Swartz, Natasja Alexandria, Price, Capri A., Clare, Tami Lasseter Year: 2016 Nanoclays are small enough to appear optically transparent, yet they have large surface-to-volume and high aspect ratios that can significantly inhibit water diffusion when incorporated into protective coatings. Clear coatings, which minimally affect the aesthetics of metalworks, are commonly applied to outdoor metalworks, such as sculptures, to prevent and slow corrosion. In recent years, waterborne clear coatings, rather than solvent-based clear coatings, are increasingly used in many applications to reduce the quantity of volatile organic components in the formulation, yet the performance of dry films produced from waterborne colloidal suspensions is generally poorer. In this work, we aim to improve the barrier properties of a highly weatherable waterborne acrylic/polyvinylidene fluoride emulsion by adding a synthetic nanoclay, Laponite, into the formulation. To improve clay−polymer compatibility, the clay was covalently modified using an acetoxy or perfluoroalkyl silane monomer that is reactive with the hydroxyl groups at the edges of the Laponite platelets. Cation exchange on the clay faces using phosphorylcholine was conducted to increase the stability in water and characterized by zeta potential. Resulting changes in barrier properties of the polymer nanocomposite films were characterized by gravimetry, colorimetry, and electrochemical impedance spectroscopy. Surface ablation after accelerated artificial weathering was monitored by attenuated total internal reflectance Fourier transform infrared microspectroscopy and Raman microspectroscopy, thin film X-ray diffraction (TF-XRD) and gloss and thickness measurements. The composite films showed many improved properties: reduced water sensitivity and ultraviolet-induced polymer degradation, which increased the barrier properties and reduced the diffusion constants over both short- and long-term weathering studies compared with films without nanoclays. The diffusion constant measured for the highest performing composite film showed that the performance gap between relevant water- and solvent-borne coatings used to protect outdoor metals was narrowed by half. Title: Minimizing Corrosion of Outdoor Metalworks Using Dispersed Chemically Stabilized Nanoclays in Polyvinylidene Fluoride Latex Coatings Author: Swartz, Natasja Alexandria, Price, Capri A., Clare, Tami Lasseter Year: 2016 Nanoclays are small enough to appear optically transparent, yet they have large surface-to-volume and high aspect ratios that can significantly inhibit water diffusion when incorporated into protective coatings. Clear coatings, which minimally affect the aesthetics of metalworks, are commonly applied to outdoor metalworks, such as sculptures, to prevent and slow corrosion. In recent years, waterborne clear coatings, rather than solvent-based clear coatings, are increasingly used in many applications to reduce the quantity of volatile organic components in the formulation, yet the performance of dry films produced from waterborne colloidal suspensions is generally poorer. In this work, we aim to improve the barrier properties of a highly weatherable waterborne acrylic/polyvinylidene fluoride emulsion by adding a synthetic nanoclay, Laponite, into the formulation. To improve clay−polymer compatibility, the clay was covalently modified using an acetoxy or perfluoroalkyl silane monomer that is reactive with the hydroxyl groups at the edges of the Laponite platelets. Cation exchange on the clay faces using phosphorylcholine was conducted to increase the stability in water and characterized by zeta potential. Resulting changes in barrier properties of the polymer nanocomposite films were characterized by gravimetry, colorimetry, and electrochemical impedance spectroscopy. Surface ablation after accelerated artificial weathering was monitored by attenuated total internal reflectance Fourier transform infrared microspectroscopy and Raman microspectroscopy, thin film X-ray diffraction (TF-XRD) and gloss and thickness measurements. The composite films showed many improved properties: reduced water sensitivity and ultraviolet-induced polymer degradation, which increased the barrier properties and reduced the diffusion constants over both short- and long-term weathering studies compared with films without nanoclays. The diffusion constant measured for the highest performing composite film showed that the performance gap between relevant water- and solvent-borne coatings used to protect outdoor metals was narrowed by half. Close

• 6. [Article] Effects of Gramicidin-A on the Adsorption of Phospholipids to the Air–Water Interface

  Prior studies suggest that the hydrophobic surfactant proteins, SP-B and SP-C, promote adsorption of the lipids in pulmonary surfactant to an air–water interface by stabilizing a negatively curved rate-limiting ...

  Citation × Citation Citation Abstract Copy Title: Effects of Gramicidin-A on the Adsorption of Phospholipids to the Air–Water Interface Author: Biswas, Samares C., Rananavare, Shankar B., Hall, Stephen B. Year: 2005 Prior studies suggest that the hydrophobic surfactant proteins, SP-B and SP-C, promote adsorption of the lipids in pulmonary surfactant to an air–water interface by stabilizing a negatively curved rate-limiting structure that is intermediate between bilayer vesicles and the surface film. This model predicts that other peptides capable of stabilizing negative curvature should also promote lipid adsorption. Previous reports have shown that under appropriate conditions, gramicidin-A (GrA) induces dioleoyl phosphatidylcholine (DOPC), but not dimyristoyl phosphatidylcholine (DMPC), to form the negatively curved hexagonal-II (HII) phase. The studies reported here determined if GrA would produce the same effects on adsorption of DMPC and DOPC that the hydrophobic surfactant proteins have on the surfactant lipids. Small angle X-ray scattering and 31P-nuclear magnetic resonance confirmed that at the particular conditions used to study adsorption, GrA induced DOPC to form the HII phase, but DMPC remained lamellar. Measurements of surface tension showed that GrA in vesicles produced a general increase in the rate of adsorption for both phospholipids. When restricted to the interface, however, in preexisting films, GrA with DOPC, but not with DMPC, replicated the ability of the surfactant proteins to promote adsorption of vesicles containing only the lipids. The correlation between the structural and functional effects of GrA with the two phospholipids, and the similar effects on adsorption of GrA with DOPC and the hydrophobic surfactant proteins with the surfactant lipids fit with the model in which SP-B and SP-C facilitate adsorption by stabilizing a rate-limiting intermediate with negative curvature. Title: Effects of Gramicidin-A on the Adsorption of Phospholipids to the Air–Water Interface Author: Biswas, Samares C., Rananavare, Shankar B., Hall, Stephen B. Year: 2005 Prior studies suggest that the hydrophobic surfactant proteins, SP-B and SP-C, promote adsorption of the lipids in pulmonary surfactant to an air–water interface by stabilizing a negatively curved rate-limiting structure that is intermediate between bilayer vesicles and the surface film. This model predicts that other peptides capable of stabilizing negative curvature should also promote lipid adsorption. Previous reports have shown that under appropriate conditions, gramicidin-A (GrA) induces dioleoyl phosphatidylcholine (DOPC), but not dimyristoyl phosphatidylcholine (DMPC), to form the negatively curved hexagonal-II (HII) phase. The studies reported here determined if GrA would produce the same effects on adsorption of DMPC and DOPC that the hydrophobic surfactant proteins have on the surfactant lipids. Small angle X-ray scattering and 31P-nuclear magnetic resonance confirmed that at the particular conditions used to study adsorption, GrA induced DOPC to form the HII phase, but DMPC remained lamellar. Measurements of surface tension showed that GrA in vesicles produced a general increase in the rate of adsorption for both phospholipids. When restricted to the interface, however, in preexisting films, GrA with DOPC, but not with DMPC, replicated the ability of the surfactant proteins to promote adsorption of vesicles containing only the lipids. The correlation between the structural and functional effects of GrA with the two phospholipids, and the similar effects on adsorption of GrA with DOPC and the hydrophobic surfactant proteins with the surfactant lipids fit with the model in which SP-B and SP-C facilitate adsorption by stabilizing a rate-limiting intermediate with negative curvature. Close

• 7. [Article] Expanding the Versatility of Nano Assembled Capsules as Platform of Potential High Payload MRI Contrast Agents

  Magnetic resonance imaging (MRI) has become a powerful clinical modality in diagnostic medicine. It is non-invasive and offers high spatial and temporal resolution. The goal of molecular imaging is to ...

  Citation × Citation Citation Abstract Copy Title: Expanding the Versatility of Nano Assembled Capsules as Platform of Potential High Payload MRI Contrast Agents Author: Farashishiko, Annah Year: 2016 Magnetic resonance imaging (MRI) has become a powerful clinical modality in diagnostic medicine. It is non-invasive and offers high spatial and temporal resolution. The goal of molecular imaging is to reveal the pathophysiology underlying the observed anatomy and diagnose diseases. The detection of pathological biomarkers can lead to early recognition of diseases and improved monitoring for recurrence. Clinically available contrast agents are limited in their discrimination of contrast between tissues and they tend to have very high detection limits. Because biomarkers are very low in concentration there is a need for high payload deposition of contrast agent (CA) and targeted imaging. Encapsulating discrete Gd3+ chelates in nano assembled capsules (NACs) is a simple and effective method of preparing an MRI contrast agent capable of delivering a large payload of high relaxivity imaging agent. The preparation of contrast agent containing NACs had previously focused on preparations incorporating GdDOTP5- into the internal aggregate. In this report we demonstrate that other Gd3+ chelates bearing overall charges as low as 2- can also be used to prepare NACs. This discovery opens up the possibility of using Gd3+ chelates that have inner-sphere water molecules that could further increase the relaxivity enhancement associated with the long rotational correlation time (TR) that arises from encapsulation. However, encapsulation of the q = 1 chelate GdDTPA2- afforded the same increase in relaxivity as the outer-sphere chelate GdTTHA3-. This leads us to the conclusion that in the NAC interior proton transport is not mediated by movement of whole water molecules and the enhanced relaxivity of Gd3+ chelate encapsulated within NACs arises primarily from second sphere effects. The nano assembled capsule platform has been further expanded by an alternative coating method, a new cross linked peptidic shell reported in this work affords robust capsules and exceptionally high per Gd3+ relaxivities (70.7 mM-1s-1). The availability of free amines on the surface of these capsules can be exploited to attach targeting moieties. This was demonstrated through the reaction of fluorescein isothiocyanate (FITC), an intense green emitting dye, with these amines. Green emission from the capsules indicated that surface amines were accessible to FITC. Unlike T1-shortening contrast agents, paraCEST agents can be switched on and off by the imaging scientist by turning on and off a pre-saturation pulse. This affords the ability to acquire both pre- and post-contrast images even after administration of a paraCEST contrast agent. This could potentially eliminate problems co-registering pre- and post-contrast images. A reverse NAC may allow a cationic paraCEST contrast agent to be incorporated in a high payload NAC. We were successful in synthesizing a reverse capsule using DyDOTAM3+, a paraCEST agent, and the negatively charged polymer polyacrylate and encapsulated with SiO2 nanoparticles. These initial preparations of reverse NACs were not able to generate CEST contrast however. Title: Expanding the Versatility of Nano Assembled Capsules as Platform of Potential High Payload MRI Contrast Agents Author: Farashishiko, Annah Year: 2016 Magnetic resonance imaging (MRI) has become a powerful clinical modality in diagnostic medicine. It is non-invasive and offers high spatial and temporal resolution. The goal of molecular imaging is to reveal the pathophysiology underlying the observed anatomy and diagnose diseases. The detection of pathological biomarkers can lead to early recognition of diseases and improved monitoring for recurrence. Clinically available contrast agents are limited in their discrimination of contrast between tissues and they tend to have very high detection limits. Because biomarkers are very low in concentration there is a need for high payload deposition of contrast agent (CA) and targeted imaging. Encapsulating discrete Gd3+ chelates in nano assembled capsules (NACs) is a simple and effective method of preparing an MRI contrast agent capable of delivering a large payload of high relaxivity imaging agent. The preparation of contrast agent containing NACs had previously focused on preparations incorporating GdDOTP5- into the internal aggregate. In this report we demonstrate that other Gd3+ chelates bearing overall charges as low as 2- can also be used to prepare NACs. This discovery opens up the possibility of using Gd3+ chelates that have inner-sphere water molecules that could further increase the relaxivity enhancement associated with the long rotational correlation time (TR) that arises from encapsulation. However, encapsulation of the q = 1 chelate GdDTPA2- afforded the same increase in relaxivity as the outer-sphere chelate GdTTHA3-. This leads us to the conclusion that in the NAC interior proton transport is not mediated by movement of whole water molecules and the enhanced relaxivity of Gd3+ chelate encapsulated within NACs arises primarily from second sphere effects. The nano assembled capsule platform has been further expanded by an alternative coating method, a new cross linked peptidic shell reported in this work affords robust capsules and exceptionally high per Gd3+ relaxivities (70.7 mM-1s-1). The availability of free amines on the surface of these capsules can be exploited to attach targeting moieties. This was demonstrated through the reaction of fluorescein isothiocyanate (FITC), an intense green emitting dye, with these amines. Green emission from the capsules indicated that surface amines were accessible to FITC. Unlike T1-shortening contrast agents, paraCEST agents can be switched on and off by the imaging scientist by turning on and off a pre-saturation pulse. This affords the ability to acquire both pre- and post-contrast images even after administration of a paraCEST contrast agent. This could potentially eliminate problems co-registering pre- and post-contrast images. A reverse NAC may allow a cationic paraCEST contrast agent to be incorporated in a high payload NAC. We were successful in synthesizing a reverse capsule using DyDOTAM3+, a paraCEST agent, and the negatively charged polymer polyacrylate and encapsulated with SiO2 nanoparticles. These initial preparations of reverse NACs were not able to generate CEST contrast however. Close

• 8. [Article] The Biomolecule Sequencer Project: Nanopore Sequencing as a Dual-Use Technology for Crew Health and Astrobiology Investigations

  Human missions to Mars will fundamentally transform how the planet is explored, enabling new scientific discoveries through more sophisticated sample acquisition and processing than can currently be implemented ...

  Citation × Citation Citation Abstract Copy Title: The Biomolecule Sequencer Project: Nanopore Sequencing as a Dual-Use Technology for Crew Health and Astrobiology Investigations Author: John, K. K., Botkin, D. S., Burton, A. S., Castro-Wallace, S. L., Chaput, J. D., Dworkin, J. P., Lehman, Niles, Lupisella, M. L., Mason, C. E., Smith, D. J., Stahl, S., Switzer, C. Year: 2016 Human missions to Mars will fundamentally transform how the planet is explored, enabling new scientific discoveries through more sophisticated sample acquisition and processing than can currently be implemented in robotic exploration. The presence of humans also poses new challenges, including ensuring astronaut safety and health and monitoring contamination. Because the capability to transfer materials to Earth will be extremely limited, there is a strong need for in situ diagnostic capabilities. Nucleotide sequencing is a particularly powerful tool because it can be used to: (1) mitigate microbial risks to crew by allowing identification of microbes in water, in air, and on surfaces; (2) identify optimal treatment strategies for infections that arise in crew members; and (3) track how crew members, microbes, and mission-relevant organisms (e.g., farmed plants) respond to conditions on Mars through transcriptomic and genomic changes. Sequencing would also offer benefits for science investigations occurring on the surface of Mars by permitting identification of Earth-derived contamination in samples. If Mars contains indigenous life, and that life is based on nucleic acids or other closely related molecules, sequencing would serve as a critical tool for the characterization of those molecules. Therefore, spaceflight-compatible nucleic acid sequencing would be an important capability for both crew health and astrobiology exploration. Advances in sequencing technology on Earth have been driven largely by needs for higher throughput and read accuracy. Although some reduction in size has been achieved, nearly all commercially available sequencers are not compatible with spaceflight due to size, power, and operational requirements. Exceptions are nanopore-based sequencers that measure changes in current caused by DNA passing through pores; these devices are inherently much smaller and require significantly less power than sequencers using other detection methods. Consequently, nanopore-based sequencers could be made flight-ready with only minimal modifications. Title: The Biomolecule Sequencer Project: Nanopore Sequencing as a Dual-Use Technology for Crew Health and Astrobiology Investigations Author: John, K. K., Botkin, D. S., Burton, A. S., Castro-Wallace, S. L., Chaput, J. D., Dworkin, J. P., Lehman, Niles, Lupisella, M. L., Mason, C. E., Smith, D. J., Stahl, S., Switzer, C. Year: 2016 Human missions to Mars will fundamentally transform how the planet is explored, enabling new scientific discoveries through more sophisticated sample acquisition and processing than can currently be implemented in robotic exploration. The presence of humans also poses new challenges, including ensuring astronaut safety and health and monitoring contamination. Because the capability to transfer materials to Earth will be extremely limited, there is a strong need for in situ diagnostic capabilities. Nucleotide sequencing is a particularly powerful tool because it can be used to: (1) mitigate microbial risks to crew by allowing identification of microbes in water, in air, and on surfaces; (2) identify optimal treatment strategies for infections that arise in crew members; and (3) track how crew members, microbes, and mission-relevant organisms (e.g., farmed plants) respond to conditions on Mars through transcriptomic and genomic changes. Sequencing would also offer benefits for science investigations occurring on the surface of Mars by permitting identification of Earth-derived contamination in samples. If Mars contains indigenous life, and that life is based on nucleic acids or other closely related molecules, sequencing would serve as a critical tool for the characterization of those molecules. Therefore, spaceflight-compatible nucleic acid sequencing would be an important capability for both crew health and astrobiology exploration. Advances in sequencing technology on Earth have been driven largely by needs for higher throughput and read accuracy. Although some reduction in size has been achieved, nearly all commercially available sequencers are not compatible with spaceflight due to size, power, and operational requirements. Exceptions are nanopore-based sequencers that measure changes in current caused by DNA passing through pores; these devices are inherently much smaller and require significantly less power than sequencers using other detection methods. Consequently, nanopore-based sequencers could be made flight-ready with only minimal modifications. Close

• 9. [Article] The Application of Electrochemical Impedance Spectroscopy to Immediately Diagnose the Protective Quality of Coatings on Artistic and Architectural Metalwork

  Corrosion is a spontaneous process that causes irreversible damage to nearly all metals, which has world-wide implications for architectural and artistic metalwork, such as bridges, buildings, airplanes ...

  Citation × Citation Citation Abstract Copy Title: The Application of Electrochemical Impedance Spectroscopy to Immediately Diagnose the Protective Quality of Coatings on Artistic and Architectural Metalwork Author: Hosbein, Kathryn Nicole Year: 2016 Corrosion is a spontaneous process that causes irreversible damage to nearly all metals, which has world-wide implications for architectural and artistic metalwork, such as bridges, buildings, airplanes and sculptures. Protective coatings such as wax, paint, or polymeric clear coatings are used to prolong the lifetime of metals such as steel and bronze. Unfortunately, these coatings fail over time due to oxidative damage by UV rays and by failure to exclude water that can carry salts and pollutants that cause corrosion of the underlying substrate. The current method of coating assessment is visual inspection but when coating failure is detected at this stage, irreversible damage has already occurred to the metal substrate. Diagnosing coating quality on artistic metalwork is a unique challenge as it requires a method that is non-destructive as to not alter the aesthetic of the piece. A non-destructive technique or device that can detect early signs of coating failure in the field (such as at a sculpture park) does not currently exist. The aim of this thesis is to develop a method that can be readily used in the field by a conservator to quickly diagnose the protective state of a coating on a sculpture in order to provide localized treatment. Electrochemical impedance spectroscopy (EIS) is a method currently used to study protective coatings in the lab. The technique itself is non-destructive but the most common electrochemical cell used with it must be used on a planar substrate and requires that a portion of coating be removed. Not only is the current method destructive, but the data produced by EIS is complicated and time consuming to analyze. These issues provide the foundation for this project. This thesis first proposes multiple methods to quickly analyze the complicated data traditionally collected through EIS. Three quick analysis methods, including the estimation of the derivative at one single frequency in EIS spectra, was successfully used to categorize coating quality of five different coating types. Using this quick analysis can aid conservators in assessing coating condition without the need for extensive training in EIS data interpretation. This thesis also proposes a method to measure early warning signs of coating degradation through a co-planar hydrogel electrochemical cell paired with EIS. The configuration of this co-planar hydrogel cell negates the need for the removal of the coating and can be used on multiple types of surfaces because of its flexibility, therefore overcoming the drawbacks of the traditional EIS electrochemical cell. Data provided demonstrates that this co-planar hydrogel provides similar information, when compared to the standard electrochemical cell, about the bulk of the protective coating. Unique to the co-planar hydrogel cell, information about surface degradation is provided during EIS measurements. This provides a warning sign before bulk degradation of the coating and therefore before any damage to the underlying substrate has occurred. Title: The Application of Electrochemical Impedance Spectroscopy to Immediately Diagnose the Protective Quality of Coatings on Artistic and Architectural Metalwork Author: Hosbein, Kathryn Nicole Year: 2016 Corrosion is a spontaneous process that causes irreversible damage to nearly all metals, which has world-wide implications for architectural and artistic metalwork, such as bridges, buildings, airplanes and sculptures. Protective coatings such as wax, paint, or polymeric clear coatings are used to prolong the lifetime of metals such as steel and bronze. Unfortunately, these coatings fail over time due to oxidative damage by UV rays and by failure to exclude water that can carry salts and pollutants that cause corrosion of the underlying substrate. The current method of coating assessment is visual inspection but when coating failure is detected at this stage, irreversible damage has already occurred to the metal substrate. Diagnosing coating quality on artistic metalwork is a unique challenge as it requires a method that is non-destructive as to not alter the aesthetic of the piece. A non-destructive technique or device that can detect early signs of coating failure in the field (such as at a sculpture park) does not currently exist. The aim of this thesis is to develop a method that can be readily used in the field by a conservator to quickly diagnose the protective state of a coating on a sculpture in order to provide localized treatment. Electrochemical impedance spectroscopy (EIS) is a method currently used to study protective coatings in the lab. The technique itself is non-destructive but the most common electrochemical cell used with it must be used on a planar substrate and requires that a portion of coating be removed. Not only is the current method destructive, but the data produced by EIS is complicated and time consuming to analyze. These issues provide the foundation for this project. This thesis first proposes multiple methods to quickly analyze the complicated data traditionally collected through EIS. Three quick analysis methods, including the estimation of the derivative at one single frequency in EIS spectra, was successfully used to categorize coating quality of five different coating types. Using this quick analysis can aid conservators in assessing coating condition without the need for extensive training in EIS data interpretation. This thesis also proposes a method to measure early warning signs of coating degradation through a co-planar hydrogel electrochemical cell paired with EIS. The configuration of this co-planar hydrogel cell negates the need for the removal of the coating and can be used on multiple types of surfaces because of its flexibility, therefore overcoming the drawbacks of the traditional EIS electrochemical cell. Data provided demonstrates that this co-planar hydrogel provides similar information, when compared to the standard electrochemical cell, about the bulk of the protective coating. Unique to the co-planar hydrogel cell, information about surface degradation is provided during EIS measurements. This provides a warning sign before bulk degradation of the coating and therefore before any damage to the underlying substrate has occurred. Close

• 10. [Article] A Facile Route to Tailoring Peptide-Stabilized Gold Nanoparticles Using Glutathione as a Synthon

  The preparation of gold nanoparticles (AuNPs) of high purity and stability remains a major challenge for biological applications. This paper reports a simple synthetic strategy to prepare water-soluble ...

  Citation × Citation Citation Abstract Copy Title: A Facile Route to Tailoring Peptide-Stabilized Gold Nanoparticles Using Glutathione as a Synthon Author: Ho Wu, Rosina, Nguyen, Tan P., Marquart, Grant W., Miesen, Thomas J., Mau, Theresa, Mackiewicz, Marilyn R. Year: 2014 The preparation of gold nanoparticles (AuNPs) of high purity and stability remains a major challenge for biological applications. This paper reports a simple synthetic strategy to prepare water-soluble peptide-stabilized AuNPs. Reduced glutathione, a natural tripeptide, was used as a synthon for the growth of two peptide chains directly on the AuNP surface. Both nonpolar (tryptophan and methionine) and polar basic (histidine and dansylated arginine) amino acids were conjugated to the GSH-capped AuNPs. Ultracentrifugation concentrators with polyethersulfone (PES) membranes were used to purify precursor materials in each stage of the multi-step synthesis to minimize side reactions. Thin layer chromatography, transmission electron microscopy, UV-Visible, 1H-NMR, and fluorescence spectroscopies demonstrated that ultracentrifugation produces high purity AuNPs, with narrow polydispersity, and minimal aggregation. More importantly, it allows for more control over the composition of the final ligand structure. Studies under conditions of varying pH and ionic strength revealed that peptide length, charge, and hydrophobicity influence the stability as well as solubility of the peptide-capped AuNPs. The synthetic and purification strategies used provide a facile route for developing a library of tailored biocompatible peptide-stabilized AuNPs for biomedical applications. Title: A Facile Route to Tailoring Peptide-Stabilized Gold Nanoparticles Using Glutathione as a Synthon Author: Ho Wu, Rosina, Nguyen, Tan P., Marquart, Grant W., Miesen, Thomas J., Mau, Theresa, Mackiewicz, Marilyn R. Year: 2014 The preparation of gold nanoparticles (AuNPs) of high purity and stability remains a major challenge for biological applications. This paper reports a simple synthetic strategy to prepare water-soluble peptide-stabilized AuNPs. Reduced glutathione, a natural tripeptide, was used as a synthon for the growth of two peptide chains directly on the AuNP surface. Both nonpolar (tryptophan and methionine) and polar basic (histidine and dansylated arginine) amino acids were conjugated to the GSH-capped AuNPs. Ultracentrifugation concentrators with polyethersulfone (PES) membranes were used to purify precursor materials in each stage of the multi-step synthesis to minimize side reactions. Thin layer chromatography, transmission electron microscopy, UV-Visible, 1H-NMR, and fluorescence spectroscopies demonstrated that ultracentrifugation produces high purity AuNPs, with narrow polydispersity, and minimal aggregation. More importantly, it allows for more control over the composition of the final ligand structure. Studies under conditions of varying pH and ionic strength revealed that peptide length, charge, and hydrophobicity influence the stability as well as solubility of the peptide-capped AuNPs. The synthetic and purification strategies used provide a facile route for developing a library of tailored biocompatible peptide-stabilized AuNPs for biomedical applications. Close