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Christopher J Orendorff

Publications and source records attributed to Christopher J Orendorff.

15 recordsLinked to original sources
PubMed2006

One-dimensional colloidal gold and silver nanostructures.

One-dimensional (1-D) metallic nanoscale materials have long been of interest to many groups of scientists. Within the last 2 decades, great advances in the synthesis of metallic nanorods and nanowires have been made, with a variety of templating methods. More recently, bottom-up chemical syntheses of these materials have become increasingly reported in the literature. This Forum Article describes the synthesis, physical properties, and potential applications of 1-D metals, with an emphasis on silver and gold derived from studies in the authors' laboratories.

Journal Article↗
PubMed2006

Structure-function relationships in high-density docosylsilane bonded stationary phases by Raman spectroscopy and comparison to octadecylsilane bonded stationary phases.

Raman spectroscopy is used to investigate the effects of temperature, surface coverage, polymerization method (surface or solution polymerized), and nature of the alkylsilane precursor on alkyl chain conformational order in a series of high-density docosylsilane (C22) stationary phases at surface coverages ranging from 3.61 to 6.97 mumol/m(2). The results of this study contribute to an enhanced understanding of the shape-selective retention characteristics of these phases at a molecular level. Conformational order is evaluated using the intensity ratio of the antisymmetric and symmetric nu(CH2) modes as well as the frequency at which these modes are observed. Alkyl chain order is shown to be dependent on surface coverage, alkyl chain length, and polymerization method. In general, alkyl chain order increases with surface coverage. Temperature-induced changes are observed between 250 and 350 K for the three phases with surface coverages between 3.61 and 4.89 mumol/m(2). These changes occur over a broad range of temperatures characteristic of two-dimensional systems, but in general adhere to the behavior predicted for a simple first-order transition. This change is not believed to be an abrupt cooperative disassociation characteristic of a phase transition in a bulk phase, but instead is thought to involve significant changes in conformational order in segments of the surface-tethered molecules, mostly those segments at the outer edge of the alkylsilane. In contrast to the changes observed in coverages below 5 mumol/m(2), a first-order change is not observed for the stationary phase with coverage of 6.97 mumol/m(2). A molecular picture of the temperature-induced disorder is proposed with disorder originating at the distal carbon and propagating only a short distance toward the proximal carbon. A comparison is made between these C22 stationary phases and similar high-density octadecylsilane (C18) bonded phases.

Journal Article↗
PubMed2006

Quantitation of metal content in the silver-assisted growth of gold nanorods.

The seed-mediated approach to making gold nanorods in aqueous surfactant solutions has become tremendously popular in recent years. Unlike the use of strong chemical reductants to make spherical gold nanoparticles, the growth of gold nanorods requires weak reducing conditions, leading to an unknown degree of gold reduction. The metal content of gold nanorods, made in high yield in the presence of silver ion, is determined by inductively coupled plasma atomic emission spectroscopy. Through the use of the known gold concentration in nanorods, molar extinction coefficients are calculated for nanorods of varying aspect ratios from 2.0 to 4.5. The extinction coefficients at the longitudinal plasmon band peak maxima for these nanorods vary from 2.5x10(9) to 5.5x10(9) M-1 cm-1, respectively, on a per-particle basis. Many of the gold ions present in the growth solution remain unreacted; insights into the growth mechanism of gold nanorods are discussed.

Journal Article↗
PubMed2005

Aspect ratio dependence on surface enhanced Raman scattering using silver and gold nanorod substrates.

Silver and gold nanorods with aspect ratios from 1 to 16 have been used as substrates for surface enhanced Raman spectroscopy (SERS) in colloidal solution. The nanorod aspect ratio is varied to give different degrees of overlap between the nanorod longitudinal plasmon band and excitation source in order to determine its effect on overall surface enhancement. Results suggest that enhancement factors are a factor of 10-10(2) greater for substrates that have plasmon band overlap with the excitation source than for substrates whose plasmon bands do not.

Colloids↗
PubMed2005

Alkylsilane-based stationary phases via a displaceable surface template approach: synthesis, characterization, and chromatographic performance.

A method is presented for the preparation of silica-based alkylsilane stationary phases using octanol as a displaceable surface template to control the rate of alkylsilane condensation with the silica surface, and thereby, the resulting alkylsilane surface coverage. This method improves upon conventional preparation schemes by allowing alkylsilane stationary phases of systematically varying surface coverage to be prepared from a single reaction mixture and a single precursor molecule without rigorous control of water content of the solution or of the silica. Octadecylsilane stationary phases ranging in surface coverage from approximately 3.5 to 6.0 micromol/m(2) were synthesized using one set of experimental conditions with variation of only the octadecylsilane/octanol ratio. The conformational order of the octadecylsilane alkyl chains was assessed using Raman spectroscopy and was found to increase with increasing surface coverage in a manner similar to stationary phases prepared by conventional routes. As chromatographic stationary phases in microbore columns for the reversed-phase separation of monosubstituted aromatic compounds, the performance of these materials is comparable to or better than that of commercially available octadecylsilane stationary phases under identical chromatographic conditions. Furthermore, the high-density stationary phases (>3.5 micromol/m(2)) prepared by this route exhibit geometric shape selectivity comparable to or better than that reported earlier for high-density octadecylsilane stationary phases prepared using conventional methods.

Journal Article↗
PubMed2005

Anisotropic metal nanoparticles: Synthesis, assembly, and optical applications.

This feature article highlights work from the authors' laboratories on the synthesis, assembly, reactivity, and optical applications of metallic nanoparticles of nonspherical shape, especially nanorods. The synthesis is a seed-mediated growth procedure, in which metal salts are reduced initially with a strong reducing agent, in water, to produce approximately 4 nm seed particles. Subsequent reduction of more metal salt with a weak reducing agent, in the presence of structure-directing additives, leads to the controlled formation of nanorods of specified aspect ratio and can also yield other shapes of nanoparticles (stars, tetrapods, blocks, cubes, etc.). Variations in reaction conditions and crystallographic analysis of gold nanorods have led to insight into the growth mechanism of these materials. Assembly of nanorods can be driven by simple evaporation from solution or by rational design with molecular-scale connectors. Short nanorods appear to be more chemically reactive than long nanorods. Finally, optical applications in sensing and imaging, which take advantage of the visible light absorption and scattering properties of the nanorods, are discussed.

Anisotropy↗
PubMed2005

Surface-enhanced Raman spectroscopy of self-assembled monolayers: sandwich architecture and nanoparticle shape dependence.

Surface enhanced Raman scattering (SERS) spectra of 4-mercaptobenzoic acid (4-MBA) self-assembled monolayers (SAMs) on gold substrates is presented for SAMs onto which gold nanoparticles of various shapes have been electrostatically immobilized. SERS spectra of 4-MBA SAMs are enhanced in the presence of immobilized gold nanocrystals by a factor of 10(7)-10(9) relative to 4-MBA in solution. Large enhancement factors are a likely result of plasmon coupling between the nanoparticles (localized surface plasmon) and the smooth gold substrate (surface plasmon polariton), creating large localized electromagnetic fields at their interface, where 4-MBA molecules reside in this sandwich architecture. Moreover, enhancement factors depend on nanoparticle shape and vary by a factor of 10(2). This SERS geometry offers large surface enhancements for molecules adsorbed onto planar substrates and could be quite useful for determining chemical information for poor Raman scatterers from assays on 2-D substrates.

Journal Article↗
PubMed2005

Raman spectroscopic study of the conformational order of octadecylsilane stationary phases: effects of electrolyte and pH.

This study investigates effects of the electrolyte, of acidic and basic compounds, and of pH on the rotational and conformational order of octadecylsilane stationary phases with surface coverages of 3.09 and 6.45 micromol/m(2). Both phases exhibit an increase in alkyl chain rotational and conformational order in 5-200 mM aqueous electrolyte solutions relative to water. These stationary phases are effectively "salted-out" of aqueous electrolyte solutions, thereby causing alkyl chain intermolecular interactions to increase with a concomitant increase in alkyl chain order. Although the presence of acidic and basic compounds generally has no effect on the conformational order of either stationary phase as a function of pH, the higher coverage stationary phase does exhibit pH-dependent changes in aqueous solutions of benzoic acid. At pH values below the pK(a) of benzoic acid, the conformational order of this stationary phase is unchanged relative to that observed in the same pH solution in the absence of benzoic acid. In light of independent evidence that such monosubstituted aromatics interact with the octadecylsilane stationary phase under these conditions, the absence of a measurable effect on alkyl chain order for these conditions is attributed to benzoic acid self-association at the stationary phase-mobile phase interface. In contrast, at pH values above the pK(a) of benzoic acid, slight disordering of the alkyl chains is observed and is attributed to repulsive interactions between retained benzoate anions.

Electrolytes↗
PubMed2005

pH-triggered assembly of gold nanorods.

The self-assembly of surfactant-protected gold nanorods (aspect ratio 3.3 +/- 0.3, 20.6 +/- 5.5 nm width, and 67.5 +/- 9.0 nm length) into ordered structures using adipic acid is presented. As made, the gold nanorods are coated with cationic surfactant, which gives them a net positive charge in aqueous solution. The pH-dependent assembly is directed by electrostatic interactions between the positively charged nanorods and negatively charged, deprotonated adipic acid. Absorption spectra and light scattering measurements of these nanorods suggest that aggregation is initiated in solution in the presence of adipic acid at pH 7-8, but not at pH 3, to form small assemblies of nanorods. Zeta potential measurements show that the assembly is significantly less positively charged in the presence of deprotonated adipic acid than when adipic acid is fully protonated.

Journal Article↗
PubMed2004

Immobilization of gold nanorods onto acid-terminated self-assembled monolayers via electrostatic interactions.

We report the immobilization of gold nanorods onto self-assembled monolayers (SAMs) of 16-mercaptohexadecanoic acid (16-MHA). The simple two step protocol involves formation of a SAM of 16-MHA molecules onto gold-coated glass slides and subsequent immersion of these slides into the gold nanorod solution. The nanorods, formed by a seed-mediated, surfactant-assisted synthesis protocol, are stabilized in solution due to surface modification by the surfactant cetyltrimethylammonium bromide (CTAB). Attractive electrostatic interactions between the carboxylic acid group on the SAM and the positively charged CTAB molecules are likely responsible for the nanorod immobilization. UV-vis spectroscopy has been used to follow the kinetics of the nanorod immobilization. The nature of interaction between the gold nanorods and the 16-MHA SAM has been probed by Fourier transform infrared spectroscopy (FTIR). The surface morphology of the immobilized rods is studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements. SEM was also used to determine the density of the immobilized nanorods as a function of the pH of immobilization. Control over the surface coverage of the immobilized gold nanorods has been demonstrated by simple pH variation. Such well-dispersed immobilized gold nanorods with control over the surface coverage could be interesting substrates for applications such as surface-enhanced Raman spectroscopy (SERS).

Journal Article↗
PubMed2003

Structure-function relationships in high-density octadecylsilane stationary phases by Raman spectroscopy. 3. Effects of self-associating solvents.

Raman spectroscopy is used to examine the subtle effects of polar, hydrogen-bonding solvents; temperature; and the surface grafting method (surface- or solution-polymerized) on alkyl chain rotational and conformational order in a series of high-density octadecylsilane stationary phases ranging in surface coverage from 3.09 to 6.45 micromol/m2. Rotational and conformational order is assessed using the intensity ratio of the antisymmetric to symmetric v(CH2) modes as well as the frequencies at which these Raman bands are observed. Alkyl rotational and conformational order decreases with decreasing surface coverage in these polar solvents, consistent with the behavior of these materials in air. For homogeneously distributed, high surface coverage materials, these polar solvents induce rotational ordering that is proposed to be due to the self-association of these solvents through hydrogen bonding or other dipole interactions at the alkylsilane-solvent interface. From these observations, molecular pictures of these solvent-stationary-phase interfaces are proposed in which solvent interaction with the stationary phase occurs primarily at the distal methyl group of the alkyl chains.

Journal Article↗
PubMed2003

Structure-function relationships in high-density octadecylsilane stationary phases by Raman spectroscopy. 4. Effects of neutral and basic aromatic compounds.

The effects of aromatic compounds (toluene, benzene, p-xylene, anisole, aniline, and pyridine), temperature, and surface grafting method (surface- or solution-polymerized) on alkyl chain rotational and conformational order in a series of high-density octadecylsilane stationary phases ranging in surface coverage from 3.09 to 6.45 micromol/m2 are examined by Raman spectroscopy. Rotational and conformational order are assessed using the intensity ratio of the antisymmetric to symmetric v(CH2) modes as well as the frequency at which the symmetric v(CH2) band is observed. Alkyl rotational and conformational order decrease with decreasing surface coverage in these aromatic compounds, which is consistent with the behavior of these materials in air and in other solvents. In addition, order of the alkyl chains is dependent on solvent hydrophobicity, hydrogen-bonding ability, and basicity. The most hydrophobic compounds impart disorder to the stationary phase; the hydrogen-bonding aromatics increase the rotational order of homogeneously distributed, high-surface-coverage materials; and basic aromatic compounds increase the conformational order of high- and low-coverage materials as the basic compounds undergo silanophilic interactions with exposed surface silanols. From these observations, molecular pictures of the chromatographic interface that display interactions between the alkyl chains and these aromatic compounds are proposed.

Journal Article↗
PubMed2002

Structure-function relationships in high-density octadecylsilane stationary phases by Raman spectroscopy. 1. Effects of temperature, surface coverage, and preparation procedure.

Raman spectroscopy is used to examine the effects of temperature, surface coverage, nature of the alkylsilane precursor (octadecyltrichlorosilane, methyloctadecyldichlorosilane, or dimethyloctadecylchlorosilane), and surface grafting method (surface or solution polymerized) on alkyl chain conformational order in a series of high-density octadecylsilane stationary phases ranging in surface coverage from 3.09 to 6.45 micromol/m2. Conformational order is assessed using the intensity ratio of the antisymmetric and symmetric v(CH2) modes as well as the frequency at which these Raman bands are observed. Conformational order increases with surface coverage. Temperature-induced surface phase changes are observed between 258 and 343 K for this homologous series of stationary phases that are demonstrated to adhere to the Clapeyron equation for a simple first-order transition. Phase changes are discussed in terms of variation of the molar enthalpy, molar entropy, and molar volume of the stationary phase, all of which depend on surface coverage. For the limited range of systems investigated, a correlation between stationary-phase preparation (surface versus solution polymerized and nature of the silane precursor) and extent of alkyl chain order is not clearly observed.Instead, akyl chain order is largely dependent on bonding density. A molecular picture of temperature-induced disorder in octadecylsilane stationary phases is proposed, with disorder originating at the distal carbon and propagating toward the proximal carbon.

Molecular Conformation↗
PubMed2002

Structure-function relationships in high-density octadecylsilane stationary phases by Raman spectroscopy. 2. Effect of common mobile-phase solvents.

Raman spectroscopy is used to examine the effects of solvent, temperature, and surface grafting method (surface or solution polymerized) on alkyl chain rotational and conformational order in a series of high-density octadecylsilane stationary phases ranging in surface coverage from 3.09 to 6.45 micromol/m2. Rotational and conformational order is assessed using the intensity ratio of the antisymmetric to symmetric v(CH2) modes as well as the frequency at which these Raman bands are observed. Solvents studied include perdeuterated hexane, toluene, chloroform, tetrahydrofuran, benzene, methanol, acetone, acetonitrile, and water. Stationary-phase order was investigated at temperatures between 258 and 323 K. Alkyl chain rotational and conformational order, and hence, solvation of the stationary phase, is dependent on solvent parameters (polarity, size, etc.), temperature, and stationary-phase properties (polymerization method and surface coverage). Information on stationary-phase conformational order allows solvent-stationary-phase interactions to be described in terms of a combination of adsorption and partitioning models for reversed-phase liquid chromatography. Finally, a distinct interplay between solvent- and temperature-induced ordering of these stationary phases is documented that is also a function of solvent and stationary-phase properties.

Molecular Conformation↗