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Biomedical subjects

W Grant McGimpsey

Publications and source records attributed to W Grant McGimpsey.

6 recordsLinked to original sources

Microscale correlation between surface chemistry, texture, and the adhesive strength of Staphylococcus epidermidis.

Staphylococcus epidermidis is among the most commonly isolated microbes from medical implant infections, particularly in the colonization of blood-contacting devices. We explored the relationships between surface wettability and root-mean-square roughness (Rq) on microbial adhesive strength to a substrate. Molecular-level interactions between S. epidermidis and a variety of chemically and texturally distinct model substrata were characterized using a cellular probe and atomic force microscopy (AFM). Substrata included gold, aliphatic and aromatic self-assembled monolayers, and polymeric and proteinaceous materials. Substrate hydrophobicity, described in terms of the water contact angle, was an insufficient parameter to explain the adhesive force of the bacterium for any of the surfaces. Correlations between adhesion forces and Rq showed weak relationships for most surfaces. We used an alternate methodology to characterize the texture of the surface that is based on a fractal tiling algorithm applied to images of each surface. The relative area as a function of the scale of observation was calculated. The discrete bonding model (DBM) was applied, which describes the area available for bonding interactions over the full range of observational scales contained in the measured substrate texture. Weak negative correlations were obtained between the adhesion forces and the area available for interaction, suggesting that increased roughness decreases bacterial adhesion when nano- to micrometer scales are considered. We suggest that modification of the DBM is needed in order to include discontinuous bonding. The adhesive strength is still related to the area available for bonding on a particular scale, but on some very fine scales, the bacteria may not be able to conform to the valleys or pits of the substrate. Therefore, the bonding between the bacterium and substrate becomes discontinuous, occurring only on the tops of ridges or asperities.

Algorithms↗

Surface-based lithium ion sensor: An electrode derivatized with a self-assembled monolayer.

Self-assembled monolayers (SAMs) of 21-(16-mercaptohexadecan-1-oyl)-4,7,13,16-tetraoxa-1,10,21-triazabicyclo[8.8.5]tricosane-19,23-dione were prepared on gold. Characterization of the SAMs was carried out by sessile drop contact angle, ellipsometry, grazing angle FT-IR spectroscopy, and electrochemical techniques. The cation recognition properties of the SAM were studied by cyclic voltammetry and impedance spectroscopy. The films show moderate selectivity for detection of Li+ ions in solution over K+ and Na+, with selectivity values calculated to be log K(Li+,Na+) approximately -1.30 and log K(Li+,K+) approximately -0.92. To the best of our knowledge, this is the first demonstration of a lithium sensor fabricated using self-assembled monolayer technology.

Journal Article↗

Non-covalent assembly of a photoswitchable surface.

A noncovalently bound multilayered thin film in which individual layers are linked by metal ligand interactions undergoes a photochemically initiated permanent change in surface wettability. The film consists of three separate layers: a SAM on gold of 4-[(10-mercaptodecyl)oxy]pyridine-2,6-dicarboxylic acid, a layer of Cu(II) ions that are deposited onto the SAM and bind symmetrically in the site provided by the two carboxylate groups and the pyridyl nitrogen atom, and a layer of cis-2,2'-dipyridylethylene, which caps the Cu(II) layer by complexation through both pyridyl nitrogen atoms (Film I). Photoexcitation of the film in chloroform at 300 nm leads to substantial cis-trans isomerization as indicated by conductivity, impedance, grazing incidence IR, and contact angle measurements. The latter show a decrease in contact angle (increase in wettability) of 17 degrees , which is attributed to exposure of both the underlying Cu(II) layer and one of the pyridyl ring nitrogen atoms following isomerization to the trans isomer.

Journal Article↗

A non-covalent strategy for the assembly of supramolecular photocurrent-generating systems.

Three photocurrent-generating thin films were assembled on gold surfaces. SAM I was constructed from molecules consisting of an alkyl disulfide group linked covalently to a 12-residue helical peptide and terminated with an alanine residue containing a pyrene chromophore. SAM I served as a benchmark for multilayered films II and III in photocurrent generation experiments. Films II and III were assembled from several components that were linked noncovalently by metal-ligand complexation. Cyclic voltammetry and contact angle measurements suggest that the films consist of ordered layers with relatively few defects. Photoexcitation of SAM I by the output of a 350 nm lamp ( approximately 0.2 mW power incident on the sample) results in current generation in the range 5-10 nA/cm2. Photoexcitation of II and III yields higher current in the range 10-30 nA/cm2, representing a quantum efficiency of approximately 1%. The observation of comparable or higher current from noncovalently assembled multicomponent films indicates that this method of assembly may obviate the problems associated with the covalent assembly of devices from large molecules.

Journal Article↗

Synthesis of an ammonium ionophore and its application in a planar ion-selective electrode.

A modular technique was used to synthesize an ammonium-selective ionophore based on a cyclic depsipeptide structure. The ionophore was incorporated into a planar ion-selective electrode sensor format and the selectivity tested versus a range of metal cations in a commercial clinical diagnostic "point-of-care" instrument. Four sensor membrane formulations were tested, all of which consisted of plasticized PVC. Formulations differed as to the type of plasticizer used and whether an ionic additive was present. It was found that the membrane containing the polar plasticizer nitrophenyl octyl ether in the absence of ionic additive exhibited near-Nernstian behavior (slope, 60.1 mV/decade at 37 degrees C) and possessed high selectivity for ammonium ion over lithium and the divalent cations, calcium and magnesium (log K(POT)NH4+(j) = -7.3, -4.4, and -7.1 for lithium, calcium, and magnesium ions, respectively). The same membrane also exhibited sodium and potassium selectivity that was comparable to that reported for nonactin (log K(POT)NH4+(j) = -2.1 and -0.6 for sodium and potassium, respectively, compared to -2.4 and -0.9 in the case of nonactin). Membranes containing the less polar plasticizer, dioctyl phthalate, showed sub-Nernstian behavior (slope, <50 mV/decade at 37 degrees C). In all cases, the presence of the ionic additive potassium tetrakis(4-chlorophenyl)borate substantially reduced the selectivity observed. The flexible modular synthetic technique developed and reported here will allow the cyclic depsipeptide structure to be tuned for optimum selectivity.

Cations↗

A highly selective bicyclic fluoroionophore for the detection of lithium ions.

The macrobicyclic molecule, 21-(9-anthrylmethyl)-4,17,13,16-tetraoxa-1,10,21-triazabicyclo [8.8.5]tricosane-19,23-dione, I, was designed, synthesized and characterized as a fluoroionophore for the selective, optical detection of lithium ions. Compound I is based on a bridged diazacrown structure, which provides a semirigid binding framework. Binding takes place by electrostatic interactions between the oxygen atoms of the crown and the cation and is transduced to fluorescence emission from an attached anthracene fluorophore. In a 75:25 dichloromethane/tetrahydrofuran solvent mixture, I acts as an intramolecular electron transfer "off-on" fluorescence switch, exhibiting a greater than 190-fold enhancement in fluorescence emission intensity in the presence of lithium ions. The relative selectivity of I for lithium ions over sodium, potassium and ammonium ions was found to be log K(Li+,Na+) approximately -3.36, log K(Li+,K+) approximately -1.77 and log K(Li+,NH4+) approximately -2.78.

Bridged Bicyclo Compounds, Heterocyclic↗