One-Pot Aldol Cascade for the Preparation of Isospiropyrans, Flavylium Salts, and bis-Spiropyrans.

We probed tandem aldol condensations of sixteen o-hydroxyacetophenones, carrying electron-withdrawing and -donating groups at positions 4 and 5, using five molar equivalents of SiCl4 in anhydrous ethanol. Substrates carrying electron-withdrawing groups (EWGs) (0 < ∑σ > 0.63) populated the equilibria with isospiropyrans (12-74% yield), while those carrying electron-donating groups (EDGs) (∑σ < -0.31) gave flavylium salts (50-80%) or thermochromic bis-spiropyrans (73%). The results are of interest for developing novel organic materials possessing switchable photochromic and thermochromic characteristics.

Inhibiting Reductive Elimination as an Intramolecular Disulfide Dramatically Enhances the Thermal Stability of SAMs on Gold Derived from Bidentate Adsorbents.

The bidentate aromatic adsorbate, 5-(octadecyloxy)-1,3-benzenedimethanethiol (R1ArmDT), with a specific design of extended S-S distance and a geometric constraint to resist cyclic disulfide formation was synthesized. The film formation and thermal stability of self-assembled monolayers (SAMs) derived from R1ArmDT were investigated and compared to those of SAMs derived from an analogous bidentate dithiol 2-(4-(octadecyloxy)-phenyl)propane-1,3-dithiol (R1ArDT), in which the two sulfur atoms can readily form a cyclic disulfide upon reductive elimination from the surface. Although the SAMs derived from R1ArmDT were less densely packed than those derived from R1ArDT, as judged by the data obtained by X-ray photoelectron spectroscopy and polarization modulation infrared reflection absorption spectroscopy, the SAMs derived from R1ArmDT were markedly more thermally stable than those derived from R1ArDT. The greater thermal stability of the R1ArmDT SAMs can be rationalized on the basis of the structure of the bidentate R1ArmDT headgroup, in which the two pendant sulfur atoms cannot access each other intramolecularly to form a cyclic disulfide upon reductive elimination from the surface.

Homogeneously Mixed Monolayers: Emergence of Compositionally Conflicted Interfaces.

The ability to manipulate interfaces at the nanoscale via a variety of thin-film technologies offers a plethora of avenues for advancing surface applications. These include surfaces with remarkable antibiofouling properties as well as those with tunable physical and electronic properties. Molecular self-assembly is one notably attractive method used to decorate and modify surfaces. Of particular interest to surface scientists has been the thiolate-gold system, which serves as a reliable method for generating model thin-film monolayers that transform the interfacial properties of gold surfaces. Despite widespread interest, efforts to tune the interfacial properties using mixed adsorbate systems have frequently led to phase-separated domains of molecules on the surface with random sizes and shapes depending on the structure and chemical composition of the adsorbates. This feature article highlights newly emerging methods for generating mixed thin-film interfaces, not only to enhance the aforementioned properties of organic thin films, but also to give rise to interfacial compositions never before observed in nature. An example would be the development of monolayers formed from bidentate adsorbates and other unique headgroup architectures that provide the surface bonding stability necessary to allow the assembly of interfaces that expose mixtures of chains that are fundamentally different in character (i.e., either phase-incompatible or structurally dissimilar), producing compositionally "conflicted" interfaces. By also exploring the prior efforts to produce such homogeneously blended interfaces, this feature article seeks to convey the relationships between the methods of film formation and the overall properties of the resulting interfaces.

Structure, Wettability, and Thermal Stability of Organic Thin-Films on Gold Generated from the Molecular Self-Assembly of Unsymmetrical Oligo(ethylene glycol) Spiroalkanedithiols.

Organic thin-films on gold were prepared from a set of new, custom-designed bidentate alkanethiols possessing a mixture of normal alkane and methoxy-terminated tri(ethylene glycol) chains. The new unsymmetrical spiroalkanedithiol adsorbates were of the form [CH3O(CH2CH2O)3(CH2)5]-[CH3(CH2)n+1]C[CH2SH]2 where n = 3 and 14; designated EG3C7-C7 and EG3C7-C18, respectively. Their corresponding self-assembled monolayers (SAMs) on gold were characterized and compared with monothiol SAMs derived from an analogous normal alkanethiol (C18SH) and an alkanethiol terminated with an oligo(ethylene glycol) (OEG) moiety (i.e., EG3C7SH). Ellipsometric data revealed reduced film thicknesses for the double-chained dithiolate SAMs, which perhaps arose from the phase-incompatible merger of a hydrocarbon chain with an OEG moiety, contributing to disorder in the films and/or an increase in chain tilt. The comparable wettabilities of the SAMs derived from EG3C7SH and EG3C7-C7, using water as the contacting liquid, are consistent with exposure of the OEG moieties at both interfaces, whereas the lower wettability of the SAM derived from EG3C7-C18 is consistent with exposure of hydrocarbon chains at the interface. The data collected by X-ray photoelectron spectroscopy confirmed the formation of the new OEG-terminated dithiolate SAMs, and also revealed them as less densely packed monolayers due in part to the large molecular cross section of the OEG moieties and to their double-chained structure with dual surface bonds. Mixed SAMs formed from pairs of monothiols having chain compositions analogous to those of the chains of the new dithiols showed that an EG3C7SH/heptanethiol-mixed SAM and the EG3C7-C7 SAM produced almost identical characterization data, revealing the favorable film formation dynamics for adsorbate structures where the alkyl chains can assemble beneath the phase-incompatible OEG termini. For the mixed SAM formed from EG3C7SH/C18SH, the data indicate that the EG3C7SH component failed to incorporate in the film, demonstrating that the blending of phase-incompatible chains is sometimes best accomplished when both chains exist on a single adsorbate structure. Furthermore, the results of solution-phase thermal desorption tests revealed that the OEG-terminated films generated from the bidentate EG3C7-C7 and EG3C7-C18 adsorbates exhibit enhanced thermal stability when compared to the film generated from monodentate EG3C7SH. In a brief study of protein adsorption, the multicomponent SAMs showed a greater ability to resist the adsorption of fibrinogen on their surfaces when compared to the SAM derived from C18SH, but not better than the monolayer derived from EG3C7SH.

Bidentate Aromatic Thiols on Gold: New Insight Regarding the Influence of Branching on the Structure, Packing, Wetting, and Stability of Self-Assembled Monolayers on Gold Surfaces.

A series of 2-phenylpropane-1,3-dithiol derivatives with single (R1ArDT), double (R2ArDT), and triple (R3ArDT) octadecyloxy chains substituted at the 4-, 3,5-, and, 3,4,5-positions, respectively, on the aromatic ring were synthesized and used to form self-assembled monolayers (SAMs) on gold. Insight into the relationship between the surface chain and headgroup packing densities was investigated by varying the number of surface chains for the bidentate adsorbates in these monolayers. Characterization of the resulting SAMs using ellipsometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, and contact angle goniometry revealed that the tailgroups become more comformationally ordered and more densely packed as the number of alkyl chains per adsorbate was increased. Conversely, the molecular packing density (i.e., number of molecules per unit area) decreased as the number of alkyl chains per adsorbate was increased. Of particular interest, the desorption profiles obtained in isooctane at 80 °C suggested that the bidentate adsorbate with the most densely packed alkyl chains, R3ArDT, was significantly more stable than the other SAMs, producing the following relative order for thermal stability for the dithiolate SAMs: R3ArDT > R2ArDT > R1ArDT.

Surface Dipoles: A Growing Body of Evidence Supports Their Impact and Importance.

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.

Robust Maleimide-Functionalized Gold Surfaces and Nanoparticles Generated Using Custom-Designed Bidentate Adsorbates.

A series of custom-designed alkanethioacetate ligands were synthesized to provide a facile method of attaching maleimide-terminated adsorbates to gold nanostructures via thiolate bonds. Monolayers on flat gold substrates derived from both mono- and dithioacetates, with and without oligo(ethylene glycol) (OEG) moieties in their alkyl spacers, were characterized using X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, ellipsometry, and contact angle goniometry. For all adsorbates, the resulting monolayers revealed that a higher packing density and more homogeneous surface were generated when the film was formed in EtOH, but a higher percentage of bound thiolate was obtained in THF. A series of gold nanoparticles (AuNPs) capped with each adsorbate were prepared to explore how adsorbate structure influences aqueous colloidal stability under extreme conditions, as examined visually and spectroscopically. The AuNPs coated with adsorbates that include OEG moieties exhibited enhanced stability under high salt concentration, and AuNPs capped with dithioacetate adsorbates exhibited improved stability against ligand exchange in competition with dithiothreitol (DTT). Overall, the best results were obtained with a chelating dithioacetate adsorbate that included OEG moieties in its alkyl spacer, imparting improved stability via enhanced solubility in water and superior adsorbate attachment owing to the chelate effect.

Semifluorinated Alkylphosphonic Acids Form High-Quality Self-Assembled Monolayers on Ag-Coated Yttrium Barium Copper Oxide Tapes and Enable Filamentization of the Tapes by Microcontact Printing.

A custom-designed semifluorinated phosphonic acid, (9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-heptadecafluorohexadecyl)phosphonic acid (F8H8PA), and a normal hexadecylphosphonic acid (H16PA) were synthesized and used to generate self-assembled monolayers (SAMs) on commercially available yttrium barium copper oxide (YBCO) tapes. In this study, we wished to evaluate the effectiveness of these monolayer films as coatings for selectively etching YBCO. Initial films formed by solution deposition and manual stamping using a non-patterned polydimethylsiloxane stamp allowed for a comparison of the film-formation characteristics. The resulting monolayers were characterized by X-ray photoelectron spectroscopy (XPS), contact angle goniometry, and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). To prepare line-patterned (filamentized) YBCO tapes, standard microcontact printing (µ-CP) procedures were used. The stamped patterns on the YBCO tapes were characterized by scanning electron microscopy (SEM) before and after etching to confirm the effectiveness of the patterning process on the YBCO surface and energy-dispersive X-ray spectroscopy (EDX) to obtain the atomic composition of the exposed interface.

Enzymatic conversion of magnetic nanoparticles to a non-magnetic precipitate: a new approach to magnetic sensing.

Magnetic sensing utilizes the detection of biomolecule-conjugated magnetic nanoparticles (MNPs). Our new strategy offers a novel approach to magnetic sensing where in situ conversion produces a "loss of signal" in the sensing device. This report demonstrates the enzymatic conversion of Fe3O4 MNPs to a non-magnetic precipitate via reduction by l-ascorbic acid generated by the action of alkaline phosphatase.

Poly(L-lysine) Interfaces via Dual Click Reactions on Surface-Bound Custom-Designed Dithiol Adsorbates.

Surfaces modified with poly(L-lysine) can be used to immobilize selected biomolecules electrostatically. This report describes the preparation of a set of self-assembled monolayers (SAMs) from three different azide-terminated adsorbates as platforms for performing controlled surface attachments and as a means of determining the parameters that afford stable poly(L-lysine)-modified SAM surfaces having controlled packing densities. A maleimide-terminated alkyne linker was "clicked" to the azide-terminated surfaces via a copper-catalyzed cycloaddition reaction to produce the attachment sites for the polypeptides. A thiol-Michael addition was then used to immobilize cysteine-terminated poly(L-lysine) moieties on the gold surface, avoiding adsorbate self-reactions with this two-step procedure. Each step in this process was analyzed by ellipsometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, and contact angle goniometry to determine which adsorbate structure most effectively produced the targeted polypeptide interface. Additionally, a series of mixed SAMs using an azidoalkanethiol in combination with a normal alkanethiol having an equivalent alkyl chain were prepared to provide data to determine how dilution of the azide reactive site on the SAM surface influences the initial click reaction. Overall, the collected data demonstrate the advantages of an appropriately designed bidentate absorbate and its potential to form effective platforms for biomolecule surface attachment via click reactions.

Boc-protected ω-amino alkanedithiols provide chemically and thermally stable amine-terminated monolayers on gold.

Four custom-designed bidentate adsorbates having either ammonium or Boc-protected amino termini and either methanethiol or ethanethioate headgroups were prepared for the purpose of generating amine-terminated self-assembled monolayers (SAMs) on evaporated gold surfaces. These adsorbates utilize a phenyl-based framework to connect the headgroups to a single hexadecyloxy chain, extending the amino functionality away from the surface of gold, providing two regions within the adsorbate structure where intermolecular interactions contribute to the stability of the fully formed thin film. The structural features of the resulting SAMs were characterized by ellipsometry, X-ray photoelectron spectroscopy, and polarization modulation infrared reflection-absorption spectroscopy. The collected data were compared to those of eight additional SAMs formed from analogous monodentate alkanethiols and alkanethioacetates having either a similar aromatic framework or a simple alkyl chain connecting the headgroup to the tailgroup. The analysis of the data obtained for the full set of SAMs revealed that both the tailgroup and headgroup influenced the formation of a well-packed monolayer, with the Boc-protected amine-terminated alkanethiols producing films with superior surface bonding and adsorbate packing as compared to those formed with ammonium tailgroups or alkanethioacetate headgroups. A comparison of the structural differences before and after deprotection of the Boc-protected amine-terminated thiolate SAMs revealed that the bidentate adsorbate was the most resistant to desorption during the Boc-deprotection procedure. Furthermore, solution-phase thermal desorption tests performed to evaluate the thermal stability of the Boc-deprotected amine-terminated alkanethiolate films provided further evidence of the enhanced stability associated with SAMs formed from these bidentate adsorbates.

Enzymatic synthesis of magnetic nanoparticles.

We report the first in vitro enzymatic synthesis of paramagnetic and antiferromagnetic nanoparticles toward magnetic ELISA reporting. With our procedure, alkaline phosphatase catalyzes the dephosphorylation of l-ascorbic-2-phosphate, which then serves as a reducing agent for salts of iron, gadolinium, and holmium, forming magnetic precipitates of Fe45±14Gd5±2O50±15 and Fe42±4Ho6±4O52±5. The nanoparticles were found to be paramagnetic at 300 K and antiferromagnetic under 25 K. Although weakly magnetic at 300 K, the room-temperature magnetization of the nanoparticles found here is considerably greater than that of analogous chemically-synthesized LnxFeyOz (Ln = Gd, Ho) samples reported previously. At 5 K, the nanoparticles showed a significantly higher saturation magnetization of 45 and 30 emu/g for Fe45±14Gd5±2O50±15 and Fe42±4Ho6±4O52±5, respectively. Our approach of enzymatically synthesizing magnetic labels reduces the cost and avoids diffusional mass-transfer limitations associated with pre-synthesized magnetic reporter particles, while retaining the advantages of magnetic sensing.

Self-assembled monolayer films derived from tridentate cyclohexyl adsorbates with alkyl tailgroups of increasing chain length.

Tridentate cyclohexyl-based alkanethiolate SAMs generated from a series of adsorbates of the form R3C6H6(CH2SH)3, where R = -(CH2)nH and n = 3, 8, and 13 (3CnCyTSH), were examined. Characterization of the SAMs by X-ray photoelectron spectroscopy (XPS) revealed that all sulfur atoms of the tridentate adsorbates were bound to the surface of gold, and that the tailgroups were in general less densely packed than the SAM derived from octadecanethiol (C18SH). For each of the SAMs, the relative molecular coverage on the surface was estimated from the XPS-derived C1s/Au4f ratios. The trend in conformational order for these SAMs as determined by the surface interactions with contacting liquids and the relative crystallinity of the alkyl chains as revealed by the PM-IRRAS spectra were found to decrease as follows: C18SH >> 3C13CyTSH > 3C8CyTSH > 3C3CyTSH. A preliminary study of the thermal stability of the SAMs as evaluated by XPS indicates that the SAM generated from the cyclohexyl-based adsorbate with the longest alkyl chain, 3C13CyTSH, is markedly more stable than the SAM generated from C18SH. Overall, the results suggest that the stability of the SAMs are influenced by both the length of the alkyl chains and the chelate effect associated with the tridentate adsorbates.

Synthesis, characterization, and relative stabilities of self-assembled monolayers on gold generated from bidentate n-alkyl xanthic acids.

A series of self-assembled monolayers (SAMs) on gold were generated by the adsorption of n-alkyl xanthic acids (NAXAs) having the general formula CH3(CH2)nOCS2H (n = 12-15). The structural features of these SAMs were characterized by optical ellipsometry, contact angle goniometry, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). This series of xanthate SAMs were compared to SAMs generated from the corresponding n-alkanethiols and aliphatic dithiocarboxylic acids (ADTCAs). The collected data indicate that the NAXAs generate densely packed and well-ordered monolayers. The contact angles of hexadecane on the xanthate monolayers exhibited a large "odd-even" effect similar to that produced by the ADTCA SAMs. The relative stability of these bidentate xanthate SAMs was evaluated by monitoring the changes in ellipsometric thicknesses and wettability as a function of time under various conditions. The results demonstrate that SAMs formed from NAXAs are much less stable than analogous n-alkanethiolate and ADTCA SAMs.

Robust carboxylic acid-terminated organic thin films and nanoparticle protectants generated from bidentate alkanethiols.

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.

Tuning the magnetic properties of nanoparticles.

The tremendous interest in magnetic nanoparticles (MNPs) is reflected in published research that ranges from novel methods of synthesis of unique nanoparticle shapes and composite structures to a large number of MNP characterization techniques, and finally to their use in many biomedical and nanotechnology-based applications. The knowledge gained from this vast body of research can be made more useful if we organize the associated results to correlate key magnetic properties with the parameters that influence them. Tuning these properties of MNPs will allow us to tailor nanoparticles for specific applications, thus increasing their effectiveness. The complex magnetic behavior exhibited by MNPs is governed by many factors; these factors can either improve or adversely affect the desired magnetic properties. In this report, we have outlined a matrix of parameters that can be varied to tune the magnetic properties of nanoparticles. For practical utility, this review focuses on the effect of size, shape, composition, and shell-core structure on saturation magnetization, coercivity, blocking temperature, and relaxation time.

Multidentate adsorbates for self-assembled monolayer films.

The spontaneous adsorption of organic molecules on a variety of planar and nonplanar substrates, that is, self assembly, can generate films just one molecule thick. These nanoscale, self-assembled monolayer (SAM) films have been extensively used to engineer surfaces with well-defined properties. Their utility has been demonstrated in a wide range of applications, including wetting, adhesion, lubrication, patterning, and molecular recognition. Many SAM systems have been investigated, but alkanethiols adsorbed on gold are the most successful combination. This pairing offers a variety of advantages, including the ability to tune precisely the interfacial properties of a surface through the well-established organic synthetic methodologies that have been developed for preparing custom ω-terminated alkanethiols. Alkanethiolate monolayers are moderately stable at room temperature; however, these films degrade over time and readily desorb upon moderate heating. This shortcoming limits the use of SAMs in applications involving elevated temperatures or harsh environments. Accordingly, new adsorbates with multiple bonding moieties have been created to enhance the stability and versatility of SAMs. In this Account, we examine a variety of multidentate adsorbate structures that have been used to generate SAMs on planar substrates and on nanoparticles. Each of these chelating adsorbates (bidentates and tridentates) has been designed to generate well-defined organic monolayer films with multiple attachment points to the underlying substrate. This bonding arrangement allows the formation of SAMs with enhanced stability through the entropy-driven "chelate effect". The research examined here demonstrates that multidentate adsorbates provide robust films: they enable the use of SAMs under conditions that are incompatible with SAMs derived from normal alkanethiols. Another advantage offered by multidentate adsorbates is the capacity for new paradigms in thin-film composition. In particular, appropriately designed chelating adsorbates can be engineered to have two or more chemically distinct terminal groups that are covalently linked to the same underlying headgroup, without adding steric bulk that might prove detrimental to the resultant assembly. This strategy allows the generation of homogeneously mixed multicomponent surfaces, overcoming the problem of phase separation or "islanding" that is pervasive when two or more chemically distinct adsorbates are used to form mixed SAMs. Such homogeneously mixed films offer the opportunity to fine-tune the interfacial properties of a substrate and to create unique heterogeneous interfaces that are well defined by the chemical composition of the tailgroups exposed at the surface. The insight derived from these studies opens the door to new uses for SAMs, both in surface engineering applications (such as corrosion resistance and soft lithographic patterning) and in the stabilization and manipulation of nanoparticles.

Fibrillar self-organization of a line-active partially fluorinated thiol within binary self-assembled monolayers.

Self-assembled monolayers (SAMs) were prepared from a novel two-tailed partially fluorinated thiol (F8C11/C16), possessing one hydrocarbon chain and one chain with an extended fluorinated segment, and from mixtures of F8C11/C16 and hexadecanethiol (C16) on gold, with the expectation that the internal chemical dissimilarity and wedge-like shape of F8C11/C16 would lead to unique self-organizational motifs. The SAMs were systematically characterized using ellipsometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), contact angle goniometry, and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). Based on this characterization, the one-component F8C11/C16 SAMs exhibited relatively poor molecular organization compared to traditional alkanethiols, forming low coverage monolayers with significant molecular disorder. However, the series of mixed SAMs formed from F8C11 and F8C11/C16 were anomalously well ordered as indicated by film thickness, surface coverage, and the frequencies of characteristic vibrational modes. AFM images of these mixed SAMs exhibited nanoscale fibrillar structures in a birds-nest morphology, suggesting that in the presence of a C16 matrix, the F8C11/C16 component organized into the two-dimensional analogue of discrete bilayers. Control experiments involving mixed SAMs comprised of F8C11/C16 and a single-tailed partially fluorinated thiol (F8C11) or C16 and F8C11 exhibited no appreciable indication of interesting self-organization beyond an evenly dispersed mixing of the thiolates or phase separation, respectively.

Self-assembled monolayers derived from alkoxyphenylethanethiols having one, two, and three pendant chains.

This article describes the design, synthesis, and study of alkoxyphenylethanethiol-based adsorbates with one (R1ArMT), two (R2ArMT), and three (R3ArMT) pendant octadecyloxy chains substituted at the 4-, 3,5-, and 3,4,5-positions, respectively, of the phenylethanethiol group. These adsorbates are being developed for use in the preparation of compositionally versatile "mixed" self-assembled monolayer (SAM) coatings. The resultant SAMs were characterized by ellipsometry, contact angle goniometry, polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). The studies revealed that R1ArMT generates a well-ordered monolayer film, while R2ArMT and R3ArMT generate monolayer films with diminished conformational order in which the degree of crystallinity decreases as follows: C18 ∼ R1ArMT > R3ArMT > R2ArMT. In addition, comparison of the molecular and chain packing densities of SAMs derived from these new adsorbates reveals that the R2ArMT and R3ArMT adsorbates give rise to SAMs with reduced chain tilt and smaller surface area per chain when compared to the SAMs derived from C18 and R1ArMT.

Optically Tunable Tin Oxide-Coated Hollow Gold-Silver Nanorattles for Use in Solar-Driven Applications.

Core@shell metal nanoparticles have emerged as promising photocatalysts because of their strong and tunable plasmonic properties; however, marked improvements in photocatalytic efficiency are needed if these materials are to be widely used in practical applications. Accordingly, the design of new and functional light-responsive nanostructures remains a central focus of nanomaterial research. To this end, we report the synthesis of nanorattles comprising hollow gold-silver nanoshells encapsulated within vacuous tin oxide shells of adjustable thicknesses (∼10 and ∼30 nm for the two examples prepared in this initial report). These composite nanorattles exhibited broad tunable optical extinctions ranging from ultraviolet to near-infrared spectral regions (i.e., 300-745 nm). Zeta potential measurements showed a large negative surface charge of approximately -35 mV, which afforded colloidal stability to the nanorattles in aqueous solution. We also characterized the nanorattles structurally and compositionally using scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Futhermore, finite-difference time-domain simulation and photoluminescence properties of the composited nanoparticles were investigated. Collectively, these studies indicate that our tin oxide-coated hollow gold-silver nanorattles are promising candidates for use in solar-driven applications.