CYP2D6*10/*10 is associated with lower steady-state plasma concentrations of active tamoxifen metabolites, which could possibly influence the clinical outcome by tamoxifen in Asian breast cancer patients.

Surface dipoles arise from differences in the distribution of electron density of interfacial molecular structures as expressed by charge separation. The direction and magnitude of the associated dipole moments directly impact a variety of interfacial phenomena. For example, the wettability of thin film-coated solid surfaces toward polar contacting liquids can be systematically adjusted by reorienting the direction of an array of interfacial dipoles, while the vector sum total of all of the dipole moments associated with such thin films can be used to tune the work function of a metal. One method of producing such dipole arrays is by coating a surface with a self-assembled monolayer (SAM), which is a thin organic film of amphiphilic adsorbates that spontaneously assemble on a surface. The interfacial properties of SAMs can be menu-selected by choice of adsorbate structure using ω-terminated thiols on gold surfaces as a convenient system for studying and utilizing these properties. In this Account, we describe the impact of an array of oriented surface dipoles upon the interfacial energy of the thin film bearing such an array. Our analysis of these films divides the subject of surface dipole arrays into three types: (1) those directing a well-defined electronegative pole toward the interface, (2) those incorporating an invertable polar group, and (3) those directing a well-defined electropositive pole toward the interface. With regard to the first category, we analyze the impact of permanent dipoles on the wettability of alkanethiolate SAMs generated from adsorbates possessing well-defined transitions between terminal fluorocarbon and underlying hydrocarbon chain segments. The second category covers recent reports of light-responsive SAMs formed from azobenzene-based adsorbates. Finally, the third category explores a unique example of a dipole array that exposes the positive ends of the interfacial dipoles formed from CH3-terminated fluorocarbon tailgroups. Our analysis of the SAMs formed from these carefully crafted adsorbates encompassing several series of fluorocarbon-containing thiols provides support for a conclusion that oriented surface dipoles exert a significant influence on interfacial energetics and wettability. In contrast to the limited distance from the interface that a surface dipole array will have upon contacting liquids, the work function of a thin film reflects the influence of all the polar groups within the film. Therefore, we also explore the change in the substrate work function for n-alkanethiol-modified gold surfaces as a function of molecular length and for other adsorbates as a function of their chemical composition.

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A new carboxylic acid-terminated alkanethiol having bidentate character, 16-(3,5-bis(mercaptomethyl)phenoxy)hexadecanoic acid (BMPHA), was designed as an absorbate and protectant to form thermally stable carboxylic acid-terminated organic thin films on flat gold and nanoparticles, respectively. The structural features of the organic thin films derived from BMPHA were characterized by ellipsometry, X-ray photoelectron spectroscopy (XPS), and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and compared to those derived from mercaptohexadecanoic acid (MHA) and 16-(4-(mercaptomethyl)phenoxy)hexadecanoic acid (MMPHA). This study demonstrates that films derived from BMPHA are less densely packed than films derived from MHA and MMPHA. However, the results of solution-phase thermal desorption tests revealed that the carboxylic acid-terminated films generated from BMPHA exhibit an enhanced thermal stability compared to those generated from MHA and MMPHA. Furthermore, as a nanoparticle protectant, BMPHA can be used to stabilize large gold nanoparticles (~45 nm diameter) in solution, and BMPHA-protected gold nanoparticles exhibited a high thermal stability in solution thermolysis studies.

The presence of surface dipoles in self-assembled monolayers (SAMs) gives rise to profound effects on the interfacial properties of the films. For example, CF3-terminated alkanethiolate films are surprisingly more wettable toward polar contacting liquids than analogous hydrocarbon SAMs due to the fluorocarbon-to-hydrocarbon transition (CF3–CH2) at the interface (i.e., the presence of a strong “FC–HC” surface dipole). This report explores the converse situation by analyzing partially fluorinated monolayers (FSAMs) in which the polarity of the surface dipole has been inverted through the creation of an “HC–FC” surface dipole. Thus, a new series of methyl-capped partially fluorinated alkanethiols, CH3(CF2)6(CH2) n SH (where n = 10–13), were designed and synthesized. Structural analyses of the new films show that these adsorbates give rise to well-ordered monolayers. As for the wetting behavior of various liquids on these FSAMs, the new films proved to be less hydrophobic than both the corresponding CF3-terminated and hydrocarbon SAMs and more oleophobic than their hydrocarbon counterparts. Furthermore, odd–even trends were observed in the wettability of the nonpolar and polar aprotic liquids on the new films in which the even FSAMs were more wettable than the odd ones for both types of liquids. However, an inverse odd–even trend was observed for polar protic liquids: odd FSAMs were more wettable than even. We attribute this latter effect to the resistance of highly hydrogen-bonded liquid molecules at the liquid–FSAM interface to adopt a more favorable orientation (on the basis of polarity) when in the presence of the inverted HC–FC dipole.