Self-assembled Monolayers Systems Research Articles

Filled and empty states of alkanethiol monolayer on Au (1 1 1): Fermi level asymmetry and implications for electron transport

The electronic structure of the prototypical self-assembled monolayer (SAM) system, i.e. alkanethiol molecules on Au, is investigated via ultraviolet and inverse photoemission spectroscopy measurements. The determination of the density of filled and empty states of the system reveals that the metal Fermi level is significantly closer to the lowest unoccupied molecular orbital (LUMO) of the molecules than to their highest occupied molecular orbital (HOMO). The results suggest that charge carrier tunneling is controlled by the LUMO, rather than by the HOMO, in contrast to what is commonly assumed.

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.

Negative Differential Resistance of Oligo(Phenylene Ethynylene) Self-Assembled Monolayer Systems: The Electric-Field-Induced Conformational Change Mechanism

We investigate here a possible mechanism for the room temperature negative differential resistance (NDR) in the Au/AN-OPE/RS/Hg self-assembled monolayer (SAM) system, where AN-OPE = 2′-amino,5′-nitro-oligo(phenylene ethynylene) and RS is a C14 alkyl thiolate. Kiehl and co-workers showed that this molecular system leads to NDR with hysteresis and sweep-rate-dependent position and amplitude in the NDR peak. To investigate a molecular basis for this interesting behavior, we combine first-principles quantum mechanics (QM) and mesoscale lattice Monte Carlo methods to simulate the switching as a function of voltage and voltage rate, leading to results consistent with experimental observations. This simulation shows how the structural changes at the microscopic level lead to the NDR and sweep-rate-dependent macroscopic I−V curve observed experimentally, suggesting a microscopic model that might aid in designing improved NDR systems.

Molecular dynamics study of the effects of chain properties on the order formation dynamics of self-assembled monolayers of long-chain molecules

The order formation dynamics of self-assembled monolayers (SAM) of long-chain molecules were studied using coarse-grained molecular dynamics simulations. The primary kinetic processes of surface order formation from solution are adsorption to the surface and surface diffusion. For long-chain molecules, the degrees of freedom of the chain structure and motion add various complexities to the order formation dynamics. Specifically, the strength of the chain interaction, the chain flexibility and the chain length play a significant role, and this work focused on the effects of these chain properties on the order formation dynamics. The adsorption dynamics of SAM molecules can be explained by the same theoretical framework as the polymer brush. On the other hand, the evolution of highly ordered structure is specific to SAM systems. Simulation results revealed that the development of oriented domains can be grouped into three types, isolated island growth, packing growth, and growth suppression, which depend on temperature and chain flexibility. In packing growth, oriented domains are formed gradually due to the decrease in free volume as the surface density becomes high, while the tilt of the adsorbed chain molecules does not become upright gradually as a whole. Rather, inside the oriented domains, the adsorbed chains adopt "standing" states with tilt angles almost equal to the final values, which contributes to the gradual increase in the total tilt order. The effect of chain length was also studied. In the case of semirigid chain molecules, longer-chain systems showed slightly slower growth in adsorption but faster growth in oriented domains. These simulation results reveal how chain properties influence the dynamics of oriented structure formation on surfaces.

Fabrication of patterned silane based self-assembled monolayers by photolithography and surface reactions on silicon-oxide substrates

Self-assembled monolayers (SAMs) have received increasing attention since their introduction 30 years ago. Soon it was discovered that they can be used as alternative resist materials and are compatible with different established lithographic techniques commonly used in silicon semiconductor technology. Besides these possibilities to structure SAMs, other attractive properties emerged from the use of SAMs. E.g., the introduction of addressability into the patterns by selective functionalization with reactive precursor molecules and/or by applying suitable surface reactions was established. In this feature we highlight developments of photolithographic techniques that have been used in combination with SAMs serving either as resists for the patterning process or as precursor molecules for surface reactions, which can be performed on non-structured and mainly photochemically structured surfaces to obtain multifunctional surfaces with tunable surface properties. The aim is to provide an overview about the versatile possibilities to use silane based SAM systems to structure silicon-oxide substrates by introducing topographical as well as chemically heterogeneous surface structures. In particular the chemical activation of SAMs includes a large number of functionalization concepts which are intended to be summarized in this review. They will be introduced here according to the class of chemical reaction that has been used. Therefore, an introduction into the plethora of possible structures, which have been created by the combination of photolithographic structuring approaches, and the integration of tailor made surface functionalities into these systems will be highlighted. Additionally effective strategies to implement a diversity of chemical functionalities onto one substrate are summarized.

Self‐Assembled Monolayers of Mono‐Tetrathiafulvalene Calix[4]pyrroles and Their Electrochemical Sensing of Chloride

Since the first reports more than a half-century ago, interest in self-assembled monolayers (SAMs) on metal surfaces has increased almost exponentially. At present, such supported SAMs are used for numerous applications, ranging from metallurgy—wherein the surface properties, such as conductivity, wettability, corrosion resistance, and etching resistance, are modified—to the preparation of sensors and materials for use in separations. In fact, the use of SAMs is now recognized as offering a convenient, flexible, and simple way to tailor the interfacial properties of metals. This is because the spontaneous organization and absorption of molecules on metal, metal oxide, or semiconducting surfaces often creates highly ordered systems with well-defined dimensions on the nanoscale. During the last decade, increasing attention has been dedicated to the design and elaboration of SAMs that integrate a molecular or ionic receptor unit with a transducer element so as to create sensing devices for environmental or biologic purposes. If a redox-active element is incorporated into the monolayer or the guest, the recognition event can be followed by cyclic voltammetry (CV). In other cases, the monitoring can be completed by using impedance spectroscopic measurements. Although, cation (generally metallic ions) recognition using SAMs is well documented, and several systems that exhibit both excellent selectivity and sensitivity have been described in the literature, much less work on anion recognition by using SAMs has been reported, perhaps reflecting the fact that anions have variable sizes and shapes and exhibit strong solvation in most solvents. The first anion recognition SAM systems were reported by Astruc et al. and involved the use of ferrocene derivatives for dihydrogenophosphate anion detection. More recently, Echegoyen et al. described SAMs for use in acetate anion recognition. Although these systems are very selective, their sensitivity is relatively low and the limits of detection do not reach the sub-millimolar scale. Calix[4]pyrrole and its derivatives have been extensively studied in the search for chemosensors capable of recognizing specific chemical species, with a number of optically active calix[4]pyrrole-based sensors having now been reported. Some of us have recently described the first fully successful examples of electrochemically active sensors based on calix[4]pyrroles; these were prepared by attaching one, two, or four redox-active tetrathiafulvalene (TTF) units directly to the calix[4]pyrrole platform so as to produce receptors with enhanced binding affinities toward anions as compared to the parent meso-octamethyl calix[4]pyrrole. In the case of the mono-TTF calix[4]pyrrole, we observed selectivity between the chloride anion (Ka= 2900m ) and the bromide anion (Ka=96m ) in CH2Cl2 solution. This success has led us to consider that TTF calix[4]pyrroles could be used to create anion-sensing SAMs. These kinds of receptors are attractive in this regard because they incorporate within one molecular framework both pyrrolebased anion recognition and TTF-derived transducer subACHTUNGTRENNUNGunits. We wish to report here that such SAMs may be prepared and that they are effective for chloride anion recognition at the sub-millimolar level, thus providing a sensitivity that differs dramatically from previously reported systems. [a] L. G. Jensen, Dr. K. A. Nielsen, Prof. J. O. Jeppesen Department of Physics and Chemistry University of Southern Denmark Campusvej 55, DK-5230, Odense M (Denmark) Fax: (+45)6615-8780 E-mail : joj@ifk.sdu.dk Homepage: http://www.jojgroup.sdu.dk [b] Dr. T. Breton, Prof. Dr. E. Levillain, Dr. L. Sanguinet Universit d’Angers—CNRS 2 boulevard Lavoisier 49045, Angers Cedex (France) E-mail : eric.levillain@iniv-angers.fr lionel.sanguinet@univ-angers.fr [c] Prof. J. L. Sessler Department of Chemistry and Biochemistry The University of Texas at Austin 1 University Station, A5300, Austin, TX 78712-0165 (USA) Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.200901394.

High-resolution X-ray photoelectron spectroscopy in studies of self-assembled organic monolayers

This article reviews recent progress in the characterization of self-assembled monolayers (SAMs) with a chalcogen headgroup by synchrotron-based high-resolution X-ray photoelectron spectroscopy (HRXPS). We present reference data for archetypical, most frequently used SAM systems and discuss specific effects and SAM properties which can only be observed at high energy resolution. We show that not only the emissions related to a SAM but also those related to the substrate can provide important information on the system under study. We demonstrate that the standard chemical shift framework is not always sufficient to explain photoemission from SAMs, but, in some selected cases, electrostatic effects should be taken into account as well. General aspects of XPS and HRXPS experiments on SAMs are discussed, including X-ray induced damage and proper calibration procedures.

Dynamics of the Reaction of O(3P) Atoms with Alkylthiol Self-assembled Monolayers

We have studied the dynamics of the reactions of O((3)P) atoms with alkylthiol self-assembled monolayers (SAMs). Superthermal O((3)P) atoms, with a fairly broad distribution of laboratory-frame kinetic energies (mean = 16 kJ mol(-1), fwhm = 26 kJ mol(-1)), were generated by 355 nm photolysis of NO(2) introduced at a low pressure above the SAM surface. Nascent OH v' = 0 products were detected by laser-induced fluorescence. SAMs of two different alkyl chain lengths, C(6) and C(18), were studied. The existence of SAM layers, and their robustness under our experimental conditions during the relevant measurement period, were confirmed by scanning-tunneling microscopy (STM). Reaction at the SAM surface was verified as the authentic source of the hydroxyl radicals using a perdeuterated C(6)D(13)-SAM sample. The OH appearance profiles as a function of photolysis-probe delay, and the rotational-state distributions at their peaks, were compared with those of liquid squalane (C(30)H(62), 2,6,10,15,19,23-hexamethyltetracosane). The reactivity of the SAMs and of squalane was found to be comparable. We conclude that the O((3)P) atoms must be able to access the more reactive secondary hydrogen atoms along the alkyl chains of the SAMs. We find no perceptible differences in reactivity or product energy disposal between the two SAM chain lengths. Both produce a substantial fraction of the OH with relatively high velocities, which must result from direct, impulsive reaction. There is also a slower component, with velocities consistent with a thermal, trapping-desorption mechanism. The proportion of this component appears to be lower for SAMs than for squalane. This would be compatible with the expected greater smoothness of the SAM surface at the molecular scale. We find little evidence for significant rotational excitation of the OH products, although the details of any correlation between translational and rotational energy release require further investigation. We compare our results with the limited available prior theoretical modeling of O((3)P) + SAM systems.

Self-Assembly of Carboranethiol Isomers on Au{111}: Intermolecular Interactions Determined by Molecular Dipole Orientations

Self-assembled monolayer (SAM) structures and properties are dominated by two interactions: those between the substrate and adsorbate and those between the adsorbates themselves. We have fabricated self-assembled monolayers of m-1-carboranethiol (M1) and m-9-carboranethiol (M9) on Au[111]. The two isomers are nearly identical geometrically, but calculated molecular dipole moments show a sizable difference at 1.06 and 4.08 D for M1 and M9 in the gas phase, respectively. These molecules provide an opportunity to investigate the effect of different dipole moments within SAMs without altering the geometry of the assembly. Pure and co-deposited SAMs of these molecules were studied by scanning tunneling microscopy (STM). The molecules are indistinguishable in STM images, and the hexagonally close-packed adlayer structures were found to have ((square root of 19) x (square root of 19))R23.4 degrees unit cells. Both SAMs display rotational domains without the protruding or depressed features in STM images associated with domain boundaries in other SAM systems. Differing orientations of molecular dipole moments influence SAM properties, including the stability of the SAM and the coverage of the carboranethiolate in competitive binding conditions. These properties were investigated by dynamic contact angle goniometry, Kelvin probe force microscopy, and grazing incidence Fourier transform infrared spectroscopy.

A molecular dynamics study on heat transfer characteristics at the interfaces of alkanethiolate self-assembled monolayer and organic solvent

In this paper, we present molecular dynamics (MD) simulations of interfaces composed of self-assembled monolayers (SAMs) and solvents in order to investigate the heat transfer characteristics at the interface. Two typical normal alkylthiolate SAMs with different chain lengths, i.e., 1-propanethiol C(3)H(7)SH and 1-dodecanethiol (C(12)H(25)SH) chemically adsorbed on Au(111) substrate surfaces, were used, and toluene was adopted as the organic solvent. In addition to the SAM systems, an interface composed of the bare solid substrate and solvent (without SAMs) was analyzed for comparison. Nonequilibrium MD simulations, in which a temperature gradient perpendicular to the interface was imposed, were performed and the difference in thermal boundary resistance in the interface systems was discussed. We observed that the SAM interfaces have smaller thermal resistance when compared with that of the bare solid interface. In order to understand the mechanisms of the small resistance at the SAM-solvent interfaces, the vibrational character of molecules in each phase, which contacted each other at the interface was analyzed and a detailed adsorbed structure of solvent molecule in the interface region was extracted. As a result, a clear difference in these characters was found between the SAM interfaces and bare solid interface.

T0501-1-6 SAM内部およびSAM界面における熱輸送特性の分子動力学的研究(マイクロ・ナノスケールの熱流体現象(1))

In this paper, we focused on heat transfer characteristics in the self-assembled monolayer (SAM) system with elucidating the dominant contribution of the molecular interactions to the heat transfer in each constituent phase, i.e., the alkanethiolate SAM phase, the interface of SAM and solvent, and alkane solvent phase. By using direct nonequilibrium molecular dynamics simulations, in which the temperature gradient was imposed across the SAM interface, each component of heat flux vector, which is transferred by molecular interactions including intra- and intermolecular interactions, were separately measured. Moreover, in order to investigate the effect of the SAM modification on thermal boundary resistance of the solid-liquid interface, the bare solid interface without the SAM was examined as well. As a result, the thermal boundary resistance at the SAM interface is much lower than that at the bare solid interface.

A Novel Isotherm, Modeling Self-Assembled Monolayer Adsorption and Structural Changes

Self-assembled monolayers (SAMs) have numerous applications, for example, engine wear inhibitors, surface profiling signal enhancement, nanostructure production, sensor production, and catalysis. The adsorbed SAM structure has a major impact on the properties of the outer monolayer surface which dictates the performance and viability of the SAM for individual applications. Substrate growth phases of SAMs have been extensively studied, and two structures have been identified. Initially, a lying down SAM structure is formed that evolves into a standing up structure. It is often critical to know how both structures form as a function of substrate immersion time to be able to design the properties of this structure. The formation of mercaptopropionic acid (MPA) SAMs on gold has been studied. Electrochemical impedance spectroscopy (EIS) was used to measure the adsorption isotherms at five temperatures in the range 4-40 degrees C. Infrared reflectance absorption spectroscopy (IRRAS) was also used, and the results show close agreement. A new monolayer adsorption isotherm is proposed which models SAM structure formation as a function of immersion time, representing all phases of SAM adsorption. This model represents a significant improvement on previous models based on Langmuir and Kisliuk adsorption isotherms that only model the fractional coverage of a surface with a SAM. The new model predicts the optimum immersion time taken for an MPA monolayer on gold to attain a surface saturated with MPA. It accounts for temperature effects on the rate of formation and the degree of monolayer disorder. It has potential for use in other SAM systems and may become the method of choice for modeling many instances of sequential substrate adsorption of two different structures, each of which exhibits different properties, as a function of immersion time.

Robust Ligand Shells for Biological Applications of Gold Nanoparticles

An important point regarding the development of stable biofunctional nanoparticles for biomedical applications is their potential for aspecific interactions with the molecules of the biological environment. Here we report a new self-assembled ligand monolayer system for gold nanoparticles called Mix-matrices, formed by a mixture of HS-PEG and alcohol peptides (peptidols) molecules. Stability of the Mix-capped nanoparticles prepared in various conditions was assessed using tests of increasing stringency. The results highlight the importance of identifying a concentration of ligands sufficiently high to obtain a compact matrix when preparing nanoparticles and that the stability of capped nanoparticles in biological environments cannot be predicted solely on their resistance to electrolyte-induced aggregation. The Mix-capped nanoparticles are resistant to aggregation induced by electrolytes and to aspecific interactions with proteins and ligand exchange. In addition, Mix-matrices allow the easy introduction of a single recognition function per nanoparticle, allowing the specific and stoichiometric labeling of proteins with gold nanoparticles. Therefore, the Mix-matrices provide a useful tool for the development of nanoparticle-based quantitative bioanalytical and imaging techniques, as well as for therapeutic purposes, such as the specific targeting of cancerous cells for photothermal destruction.

Single Component Self‐Assembled Monolayers of Aromatic Azo‐Biphenyl: Influence of the Packing Tightness on the SAM Structure and Light‐Induced Molecular Movements

AbstractAiming at modulating the packing density within functional self‐assembled monolayers (SAMs), two azo‐biphenyl derivatives AZO1 and AZO2 comprising a terminal sulfur anchor group have been designed and synthesized. While AZO1 allows for a coplanar arrangement of both biphenyl subunits, additional steric repulsion due to two methyl side groups attached to the footing biphenyl of AZO2 results in an increased intermolecular distance within the SAM, providing additional free volume. SAMs of both derivatives on gold and platinum substrates have been formed and thoroughly investigated by photoelectron (XPS) and near‐edge absorption fine structure (NEXAFS) spectroscopy as well as cyclic voltammetry and scanning tunneling microscopy. These measurements confirmed the formation of tightly packed SAMs for AZO1, while AZO2 formed SAMs consisting of less organized and more loosely packed molecules. Optical investigations of both azo derivatives in solution as well as their SAMs displayed efficient photoisomerization in solution and in SAMs. Comparable maximal cis/trans ratios of ca. 0.9 have been observed in all cases upon irradiation at λ = 370 and 360 nm for AZO1 and AZO2, respectively. The thermally induced cis → trans back reaction on AZO1 was found to be slower by a factor of 3 in SAMs as compared to solution, while AZO2 displayed comparable rates of the back reaction in both environments. This behavior can be explained by the different nature of molecular isomerization in the two SAM systems: whereas the isomerization in AZO1 SAMs takes place in a highly coordinated, collective way and involves many adjacent molecules, AZO2 species behave rather individually even packed in SAMs, such that their isomerization process is similar in SAMs and in solutions.

Synthesis of a New Organic Linker Molecule for Protein Immobilization

Recent biological and medicinal experimental techniques for diagnosis and drug discovery utilize microarrays of proteins immobilized on solid substrates. Such protein “chips” can have proteins on surface attached covalently or non-covalently between proteins and linker molecules frequently by chemisorption of the film components to the substrate from solution. For the well defined systems, organic monolayer films have formed versatile model study. The arrays of proteins attached to a solid surface have a great potential for detecting interactions of protein-ligand, proteinprotein, and antibody-antigen. Among several self-assembling systems, organosulfur compounds including dialkyl sulfides, dialkyl disulfides, and thiols have been investigated intensively on gold. It has been recognized that self-assembled monolayers (SAM) using organosufur compounds on gold are advantageous over other SAM systems because of higher structural order by densely packing long chains. In addition, versatile functionalization of terminal group at the monolayer surface suggests ideal model systems for immobilization and interfacial interaction. Several functional groups including anhydride, succinimidyl ester, maleimide, and phosphinothioester have been applied for the chemoselective binding of proteins. Here, we report a new potential substrate for the covalent and specific immobilization of nucleophilic molecules. The new organic linker, disulfide 1, has 4, 5-difluoro-2-nitroaniline amide moiety on the head and a long carbon chain with a triazole group. We envisioned that the compound would be prepared via 1,3-dipolar cycloaddition of azide 2 and alkyne 3, and hoped that a Meisenheimer complex of 4,5-difluoro-2-nitroaniline amide moiety would serve for a covalent attachment of amine or thiol moieties, and eventually proteins on the surface (Scheme 1). Prior to the synthesis of the molecule, we wanted to evaluate the reactivity of the substrate 1 toward nucleophilic aromatic substitution. Therefore, we first prepared a amide 4 from 4,5-difluoro-2-nitroaniline and 10-undecenoyl chloride and have tried the substitution reaction with various amines and a thiol as a model study (Table 1). The reaction was carried out in THF/water at room temperature. Primary and secondary amines reacted with the nitroaniline in minutes to afford good yields. Cyclic amines provided better than noncyclic secondary amines, and thiol provided the best yield in the shortest reaction time as expected. On the basis of the result, we anticipate the functional groups in proteins, amine or thiol, would show the similar reaction pattern toward the

Surface-Confined Energy Transfer in Mixed Self-Assembled Monolayers

We have fabricated a set of self-assembled monolayers consisting of naphthalene and dansyl derivatives in a range of surface loading ratios for the purpose of examining excitation transport in mixed self-assembled monolayer systems. Both tethered chromophores were immobilized on an epoxide-terminated adlayer on silica via an identical spacer, where the linking chemistry produced an amide linkage. X-ray photoelectron spectroscopy (XPS), ellipsometry, and contact angle measurements were used to characterize these chromophore-containing layers. The excitation transfer behavior of these monolayers has been examined using steady-state and time-resolved fluorescence spectroscopy. Steady-state fluorescence measurements show that excitation transfer from the naphthalene to dansyl chromophores occurs, with the efficiency of excitation transport scaling with chromophore surface loading densities, as expected. The donor lifetimes decrease with increasing acceptor loading density, and the functional form of the acceptor decay was independent of the donor/acceptor ratio. Our findings are not consistent with a homogeneous adlayer, but do provide information on the structural heterogeneity that is characteristic of these interfaces.

507 SAM-溶媒界面における界面熱抵抗特性の分子論的研究(T07-2 流体及び界面におけるナノ構造と流動特性(2),大会テーマセッション,21世紀地球環境革命の機械工学:人・マイクロナノ・エネルギー・環境)

In this paper, we perform molecular dynamics simulations of self-assembled monolayer (SAM) and solvent interfaces in order to elucidate the microscopic mechanisms of interfacial heat transfer at the SAM interfaces. Archetypal SAM systems, i.e., n-alkanethiol chemically adsorbed on Au (111), and toluene solvent are employed in our simulations. By using nonequilibrium molecular dynamics technique, a temperature gradient is imposed perpendicular to the interface, and interfacial heat transfer characteristics are analyzed. In addition to the SAM systems, a bare solid substrate and solvent system is examined to compare thermal boundary resistances at the SAM-modified interface and non-modified one. As a result, we find a significant decrease of the thermal boundary resistance at the SAM-toluene interface as compared to that of the bare Au interface. In order to explain this effect, we focus on the adsorption structure of toluene in the vicinity of the interface.

Balance of Structure−Building Forces in Selenium-Based Self-Assembled Monolayers

Using a model system of 4,4‘-biphenyl-substituted alkaneselenols on (111) gold and silver substrates, we show that the hybridization and, thus, spatial orientation of the binding orbitals of selenium is a determining factor for the molecular packing and structure of alkaneselenolate self-assembled monolayers (SAMs). Considering that a similar effect has been previously observed for the sulfur headgroup in alkanethiolate SAMs, its generality for different SAM systems can be assumed.

Surface characterization and platelet compatibility evaluation of the binary mixed self-assembled monolayers

This report describes a technique that used mixed self-assembled monolayer (SAM) as a model surface to evaluate the effect of steric hindrance on the SAM packing quality and its platelet compatibility. Two series of binary mixed SAMs were formed by mixing the bulky terminated alkanethiol (HS(CH 2) 10PO 3H 2) with a smaller terminated one (HS(CH 2) 9CH 3 and HS(CH 2) 11OH) respectively. Surface characterization results showed the hydrophilicity on these two series of mixed SAMs changed with the solution mole fraction of PO 3H 2 terminated thiol, χ PO 3H 2,soln , and reached to a nearly constant value as χ PO 3H 2,soln was 0.6 for PO 3H 2 + CH 3 SAM and 0.4 for PO 3H 2 + OH SAM. This finding should be due to the gradual saturation of surface PO 3H 2 functionality on these mixed SAMs. The XPS analysis indicated the addition of the CH 3 and OH terminated thiol could reduce the steric hindrance effect of PO 3H 2 functionality on monolayer formation and, henceforth, improve the SAM packing quality. In vitro platelet adhesion assay revealed the platelet compatibility on the PO 3H 2 + OH SAMs was better than that on the PO 3H 2 + CH 3 and the pure PO 3H 2 ones. Moreover, the PO 3H 2 + OH SAM with a low χ PO 3H 2,soln value exhibited the least platelet activating property of these two mixed SAM systems. These findings suggested that material's surface wettability and surface charge density should act collectively in affecting its platelet compatibility.

Neutral radical molecules ordered in self-assembled monolayer systems for quantum information processing

Implementation of quantum information processing based on spatially localized electronic spins in stable molecular radicals is discussed. The necessary operating conditions for such molecules are formulated in self-assembled monolayer (SAM) systems. As a model system we start with 1,3-diketone types of neutral radicals. Using first principles quantum chemical calculations we prove that these molecules have stable localized electron spin, which may represent a qubit in quantum information processing.