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SAMs of shape-persistent macrocycles: structure and binding on HOPG and Au(111).

Self-assembled monolayers of shape-persistent macrocycles have been adsorbed on highly oriented pyrolytic graphite and Au(111) substrates. Their structure and binding characteristics have been investigated by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy experiments. Special functionalization of the macrocycles for the first time has enabled their self-assembling and binding on a metal substrate and opened a new route for new functional nanostructures.

Gold↗

Direct patterning of self-assembled monolayers on gold using a laser beam.

The development of a methodology to manipulate surface properties of a self-assembled monolayer (SAM) of alkanethiol on a gold film using direct laser patterning is the objective of this paper. The present study demonstrates proof of the concept for the feasibility of laser patterning monolayers and outlines theoretical modeling of the process to predict the resulting feature size. This approach is unique in that it eliminates the need for photolithography, is noncontact, and can be extended to other systems such as SAMs on silicon wafers or potentially polymeric substrates. A homogeneous SAM made of 1-hexadecanethiol is formed on a 300-A sputtered film of gold (supported by a soda lime glass substrate). Localized regions are then desorbed by scanning the focal spot of a 488-nm continuous-wave argon ion laser beam under a nitrogen atmosphere. The desorption occurs as a result of a high substrate temperature produced by the moving laser beam with a Gaussian spatial profile at a constant speed of 200 microm/s. After completing the scans, the sample is dipped into a dilute solution of 16-mercaptohexadecanoic acid and a hydrophilic monolayer self-assembles along the previously irradiated regions. The resultant lines are viewed, and line widths are measured using both wetting with tridecane under a light microscope and scanning electron microscopy. Using the direct laser patterning method, we have produced straight line patterns with widths of 28-170 microm. A thermal model was constructed to predict the line width of the desorbed monolayer. The effect of the laser power, beam waist, and temperature dependence of the substrate conductivity on the theoretical predictions is considered. It is shown that the theoretical predictions are in good agreement with the experimental results, and, thus, the model can effectively be used to predict experimental results.

Adsorption↗

Antioxidant action by gold-PAMAM dendrimer nanocomposites.

Gold-dendrimer nanocomposites were prepared in the presence of poly(amidoamine) (PAMAM) dendrimer (generation 3, 3.5, 5, and 5.5) via reduction of HAuCl4 with sodium borohydride. The average particle size of the gold nanoparticles was independent of the dendrimer concentration, ranging between 3.0 and 4.3 nm in diameter. The catalytic activities of the gold-dendrimer nanocomposites upon elimination of hydroxyl radicals formed in an H2O2/FeSO4 system were examined using a spin-trapping method. The gold-dendrimer nanocomposites exhibited high catalytic activities which were hardly affected by the concentration and the generation of the dendrimer except PAMAM dendrimer 3.5. The highest activity for the gold-PAMAM dendrimer 3.5 nanocomposites was 85 times that of ascorbic acid.

Antioxidants↗

Polyaniline/Au composite hollow spheres: synthesis, characterization, and application to the detection of dopamine.

Polyaniline (PANI)/Au composite hollow spheres were successfully synthesized using polystyrene/sulfonated polystyrene core/shell gel particle templates. The PANI shell thickness and the number of Au nanoparticles decorating the PANI could be controlled effectively by adjusting the experimental conditions. The morphology, composition, and optical properties of the resulting products were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and ultraviolet-visible absorption spectra. It was found that the electrical conductivity of the PANI/Au composite hollow spheres was more than 3 times higher than that of the pure PANI hollow spheres. Furthermore, PANI/Au composites were immobilized on the surface of a glassy carbon electrode (GCE) and applied to construct a sensor. The obtained PANI/Au-modified GCEs showed one pair of redox peaks and high catalytic activity for the oxidation of dopamine. The possible formation mechanism of the PANI/Au composite hollow spheres was also discussed.

Aniline Compounds↗

Scanning electrochemical microscope observation of defects in a hexadecanethiol monolayer on gold with shear force-based tip-substrate positioning.

Scanning electrochemical microscopy (SECM) was used for imaging of n-hexadecanethiol-modified Au surfaces. In these studies, small defects were observed in the monolayer when a submicrometer electrode was used as an SECM tip, although a cyclic voltammogram of a Au disk electrode showed that the surface of the Au was completely covered with n-hexadecanethiol. The dependence of the SECM images on the potential of the Au electrode was also examined. A comparison of the current at the Au electrode and the tip current in the SECM images showed that direct electron transfer through the monolayer was dominant, rather than electron transfer at the defects. The size of the defects was estimated from the tip current to be 1-100 nm, under the assumption that the defects were small compared to the SECM probe.

Electrochemistry↗

Colorimetric detection of thiol-containing amino acids using gold nanoparticles.

This paper reports findings of an investigation of the unusual colorimetric change of gold nanoparticles in the presence of thiol-containing amino acids such as homocysteine, cysteine and glutathione. The colorimetric change for homocysteine exhibits a rate that is about two orders of magnitude higher than that for cysteine, and at least five orders of magnitude higher than that for glutathione. The reactivity is effectively reduced or suppressed by the coexistence of either cysteine or glutathione. It is believed that the reactivity involves encapsulation of the particles by the thiol-containing amino acids which is followed by crosslinking at the encapsulating shells. In comparison with cysteine and glutathione, homocysteine has a slower encapsulating rate but a faster crosslinking rate. Implications of the findings of the interfacial encapsulation and crosslinking reactivities of gold nanoparticles to potential nanoparticle-enhanced analytical detection of thiol-containing amino acids are also briefly discussed.

Amino Acids↗

Receptor-mediated endocytosis of alpha 2-macroglobulin and transferrin in rat caput epididymal epithelial cells in vitro.

The endocytic activity of epithelial cells from the rat epididymis in vitro has been examined by following the uptake of tracer compounds conjugated to proteins. Transferrin-gold and alpha 2-macroglobulin-gold were taken up initially in coated pits, internalized and sequestered into tubular-vesicular structures, multivesicular bodies and, in the case of alpha 2-macroglobulin, into lysosomes. Uptake could be prevented by an excess of unlabeled protein. Studies using 125I-alpha 2-macroglobulin and 125I-transferrin also showed that the uptake of these proteins was specific and could be displaced with increasing amounts of unlabeled protein. In addition, binding of 125I-transferrin to cells was saturable at 4 degrees C. These studies indicate that transferrin and alpha 2-macroglobulin are taken up by receptor-mediated endocytosis. In contrast, a fluid phase marker, bovine serum albumin-gold (BSA-gold), was initially taken up predominantly in uncoated caveolae rather than coated pits, and could not be displaced with excess BSA. By virtue of their charge, polycationized ferritin and unlabeled colloidal gold were taken up and internalized by adsorptive endocytosis, a pathway which is similar to fluid phase endocytosis. The uptake and internalization of alpha 2-macroglobulin and transferrin differed in a number of respects. Uptake and internalization of alpha 2-macroglobulin but not of transferrin was dependent on extracellular calcium. Only alpha 2-macroglobulin was transferred into lysosomes, whereas transferrin was recycled to the cell surface. Although the proton ionophore, monensin, and the transglutaminase inhibitor, dansylcadaverine, did not stop uptake and internalization of either alpha 2-macroglobulin or transferrin, they did prevent the transfer of alpha 2-macroglobulin to lysosomes.

Adsorption↗

Identifying modulators of hERG channel activity using the PatchXpress planar patch clamp.

The authors used the PatchXpress 7000A system to measure compound activity at the hERG channel using procedures that mimicked the "gold-standard" conventional whole-cell patch clamp. A set of 70 compounds, including hERG antagonists with potencies spanning 3 orders of magnitude, were tested on hERG302-HEK cells using protocols aimed at either identifying compound activity at a single concentration or obtaining compound potency from a cumulative concentration dependence paradigm. After exposure to compounds and subsequent washout of the wells to determine reversibility of the block, blockade by a reference compound served as a quality control. Electrical parameters and voltage dependence were similar to those obtained using a conventional whole-cell patch clamp. Rank order of compound potency was also comparable to that determined by conventional methods. One exception was flunarizine, a particularly lipophilic compound. The PatchXpress accurately identified the activity of 29 moderately potent antagonists, which only weakly displace radiolabeled astemizole and are false negatives in the binding assay. Finally, no false hits were observed from a collection of relatively inactive compounds. High-quality data acquisition by PatchXpress should help accelerate secondary screening for ion channel modulators and the drug discovery process.

Cell Line↗