Platelet compatibility improvement by proper choice of acidic terminal functionality for mixed-charge self-assembled monolayers

In this study two different series of mixed-charge self-assembled monolayers (SAMs) prepared with -N(+)(CH(3))(3)-terminated alkanethiol and strong dissociated monovalent -SO(3)H acid-terminated or weaker dissociated divalent -PO(3)H(2) acid-terminated alkanethiol in pure ethanol were characterized. The influence of the acidity of the anionic functionality in the mixed-charge SAMs on the surface characteristics and platelet compatibility was investigated. X-ray photoelectron spectroscopy indicated that a nearly equivalent amount of countercharged terminal groups was noted on the surface of -SO(3)H/-N(+)(CH(3))(3) mixed SAMs, while "-N(+)(CH(3))(3) thiol poor" phenomena were found on -PO(3)H(2)/-N(+)(CH(3))(3) mixed SAMs instead. This was caused by the distinct differences in solvation capability between the acidic anionic functional groups and solvent molecules and/or the interactions among the terminal ends of the thiols. This acidity difference also affected other interfacial properties and the platelet compatibility. The mixed SAMs formed from the mixture of -SO(3)H- and -N(+)(CH(3))(3)-terminated thiols showed higher surface hydrophilicity and exhibited the least amount of platelets adhered, but these two mixed SAMs were all fairly negatively surface charged. The structure of the hydration layer near the surfaces was likely affected by the acidity of the anionic functionality, and this would cause such a distinct behavior in platelet compatibility. It was concluded that the hydrophilic surfaces with nearly equal amounts of surface positively and negatively charged components could exhibit better platelet compatibility. This work demonstrated that the nature of the acidic terminal ends of alkanethiol is also a key factor for preparing mixed-charge SAMs with good platelet compatibility.     

Hydration of oligo(ethylene glycol) self-assembled monolayers studied using polarization modulation infrared spectroscopy

The interaction with water of protein-resistant monolayers (SAMs), self-assembled from (triethylene glycol) terminated thiol HS(CH2)11(OCH2CH2)3OMe solutions, was studied using in and ex situ polarization-modulated Fourier transform infrared spectroscopy. In particular, shifts in the position of the characteristic C-O-C stretching vibration were observed after the monolayers had been exposed to water. The shift in frequency increased when the SAM was observed in direct contact with a thin layer of water. It was found that the magnitude of the shift also depended on the surface coverage of the SAM. These findings suggest a rather strong interaction of oligo(ethylene glycol) SAMs with water and indicate the penetration of water into the upper region of the monolayer.     

Improving the surface biocompatibility with the use of mixed zwitterionic self-assembled monolayers prepared by a proper solvent

In this study, the mixed self-assembled monolayers (SAMs) containing the mixture of long-chain alkanethiol, SH(CH(2))(11)NH(2) and SH(CH(2))(10)SO(3)H, was prepared as a model surface to examine the interaction between the biological environment and artificial surface. The 10% (v/v) NH(4)OH ethanolic solution and DMSO were chosen as the solvents for the preparation of these mixed SAMs and the "solvent effect" was discussed. X-ray photoelectron spectroscopy (XPS) has indicated that -SO(3)H/-NH(2) mixed SAMs formed from 10% (v/v) NH(4)OH ethanolic solution were surface "-SO(3)H poor", while a nearly equivalent amount of surface -SO(3)H functionality was presented on the mixed SAMs formed from DMSO. This has resulted from the different solvation capability between solvent molecules and the alkanethiol. Such solvent effects were also reflected in various surface properties such as surface wettability and surface zeta potential. The mixed SAMs formed from DMSO were more surface hydrophilic and less negatively surface charged than from 10% (v/v) NH(4)OH ethanolic solution. In addition, these mixed SAMs formed from DMSO exhibited the least amount of protein adsorbed as well as a better platelet compatibility than its counterpart from 10% (v/v) NH(4)OH ethanolic solution. These findings indicated that choosing a proper solvent for mixed zwitterionic SAM can greatly affect its surface properties and biocompatibility, such as to form a surface with near neutrality for reducing protein adsorption and subsequent platelet adhesion and activation.     

Electrochemical release of amine molecules from carbamate-based, electroactive self-assembled monolayers

In this paper, carbamate-based self-assembled monolayers (SAMs) of alkanethiolates on gold were suggested as a versatile platform for release of amine-bearing molecules in response to the electrical signal. The designed SAMs underwent the electrochemical oxidation on the gold surface with simultaneous release of the amine molecules. The synthesis of the thiol compounds was achieved by coupling isocyanate-containing compounds with hydroquinone. The electroactive thiol was mixed with 11-mercaptoundecanol [HS(CH(2))(11)OH] to form a mixed monolayer, and cyclic votammetry was used for the characterization of the release behaviors. The mixed SAMs showed a first oxidation peak at +540 mV (versus Ag/AgCl reference electrode), indicating the irreversible conversion from carbamate to hydroquinone groups with simultaneous release of the amine molecules. The analysis of ToF-SIMS further indicated that the electrochemical reaction on the gold surface successfully released amine molecules.     

Oxidation of organic films by beams of hydroxyl radicals

We have studied the oxidation of self-assembled monolayers (SAMs) of alkanes and alkenes with a thermal beam of OH radicals. The target films were produced by bonding alkane thiols and alkene thiols to a gold surface and the SAMs are mounted in a vacuum chamber at a base pressure of 10-9 Torr. Hydroxyl radicals were produced by a corona discharge in an Ar/H2O2/water mixture. The resultant molecular beam was scanned by an electrostatic hexapole and the OH radicals [4 (+/- 1) x 1011 OH radicals cm-2 sec-1] were focused onto the target SAM. All of the hydroxyl radicals impinging on the SAM surface are rotationally (J' ' 相似文献   

Packing density of HS(CH2)(n)COOH self-assembled monolayers

Self-assembled monolayers (SAMs) of HS(CH(2))(n)COOH, n = 5, 10, 15 deposited from ethanol solution onto gold are prepared by five approaches, and their packing densities are evaluated by X-ray photoelectron spectroscopy (XPS) measurements. The five approaches are: (1) direct deposition; (2) acetic-acid-assisted deposition; (3) butyl-amine-assisted deposition; (4) displacement of a preformed HS(CH(2))(n)CH(3) (n = 5, 10, 15) SAMs; and (5) co-deposition with HS(CH(2))(n)CH(3) (n = 5, 10, 15). Packing density metrics are calculated from measurements of SAM and substrate photoemission intensities and their attenuations by two methods. In one case the attenuated photoemissions are expressed as a ratio relative to comparable measurements on an experimental HS(CH(2))(n)CH(3) model system. In the other case a new method is introduced where a calculated attenuation based on theoretical random coil and extended chain models is used as the reference to determine a packing density fraction. Packing densities are also correlated with the S2p(Au-bonded):Au4f peak area ratios and with shifts in the C1s binding energies. SAMs prepared by the direct deposition are a partial multilayer where a second molecular layer is physisorbed onto the SAM and not removable by solvent washing. The addition of acetic acid to the deposition solution disrupts dimer associations of HS(CH(2))(n)COOH in solution and at the surface of the monolayer and yields the most ordered monolayer with the highest density of -COOH groups. The addition of butyl amine results in a labile ammonium carbonate ion pair formation but results in a lower packing density in the SAM. The displacement of the preformed HS(CH(2))(n)CH(3) SAM and the co-deposition of HS(CH(2))(n)CH(3) with HS(CH(2))(n)COOH result in SAMs with little incorporation of the -COOH component.     

Spontaneous Emulsification Produced by Chemical Reactions

Self-assembled monolayer (SAM) formation of alkanethiols with ionic, hydrophilic terminal functionalities onto various O(2) plasma/ethanol pretreated gold substrates was characterized to explore the effect of gold surface oxide on the SAM packing quality. Oxygen adsorption induced by the Au(2)O(3) surface residuals are observed on the plasma-oxidized and O(2) plasma/ethanol-rinsed pretreated Au surfaces while no obvious adsorbed oxygen is found on freshly coated and O(2) plasma/ethanol sonication pretreated Au substrates. A model for the formation of hydrophilic terminated SAMs, -OH, -COOH, and -PO(3)H(2) is proposed. According to this model, the ionic and/or other binding interactions between the surface Au(2)O(3) and the alkanethiol hydrophilic terminal end as well as the interactions between the terminal SAM functionalities could cause the packing disorder found on these three SAMs formed on Au substrates containing Au(2)O(3) surface species. Copyright 2001 Academic Press.     

辛基三乙氧基硅烷/十八烷基三氯硅烷均相混合自组装单分子膜的表征及其形成机制

使用接触角、原子力显微镜(AFM)、静电力显微镜(EFM)和傅里叶变换红外(FTIR)光谱对辛基三乙氧基硅烷(C8TES)/十八烷基三氯硅烷(OTS)均相混合自组装单分子膜(SAM)及其形成过程中样品表面的润湿性、表面形貌、表面电势和膜内分子的有序度进行了表征,对采用分步法利用C8TES分子空间位阻制备C8TES/OTS均相混合SAM的反应机制进行了研究.结果表明,C8TES/OTS均相混合SAM表面接触角为105°,样品表面平整、光滑;对样品表面电势进行分析后发现,混合SAM表面电势分布均匀,电势频率分布为典型的正态分布;在均相混合SAM的形成过程中,样品表面电势的分布始终十分均匀,电势频率分布均为典型的正态分布;C8TES/OTS均相混合SAM是一种具有上下两层分子排列密度不同的膜结构的单分子膜,其内部结构至少在500 nm×500 nm到20μm×20μm尺度上是高度均匀一致的,膜内没有明显的特征结构,具有典型的均相混合SAM特征.     

辛基三乙氧基硅烷/十八烷基三氯硅烷均相混合自组装单分子膜的表征及其形成机制

使用接触角、原子力显微镜（AFM）、静电力显微镜（EFM）和傅里叶变换红外（FTIR）光谱对辛基三乙氧基硅烷（C8TES）/十八烷基三氯硅烷（OTS）均相混合自组装单分子膜（SAM）及其形成过程中样品表面的润湿性、表面形貌、表面电势和膜内分子的有序度进行了表征,对采用分步法利用C8TES分子空间位阻制备C8TES/OTS均相混合SAM的反应机制进行了研究. 结果表明,C8TES/OTS均相混合SAM表面接触角为105°,样品表面平整、光滑;对样品表面电势进行分析后发现,混合SAM表面电势分布均匀,电势频率分布为典型的正态分布;在均相混合SAM的形成过程中,样品表面电势的分布始终十分均匀,电势频率分布均为典型的正态分布;C8TES/OTS均相混合SAM是一种具有上下两层分子排列密度不同的膜结构的单分子膜,其内部结构至少在500 nm×500 nm到20 μm×20 μm尺度上是高度均匀一致的,膜内没有明显的特征结构,具有典型的均相混合SAM特征.     

Ideal nonideality in adsorption of 2-aminoethanethiol and 2-mercaptoethane sulfonic acid to form electrostatically stabilized binary self-assembled monolayers on Au(111)

In formation of binary self-assembled monolayers (SAMs) composed of 2-aminoethanethiol (AET) and 2-mercaptoethane sulfonic acid (MES) by adsorption from an ethanol solution on Au(111), the adsorption shows nearly ideal nonideality in that the surface ratio of MES to AET in the SAM is unity and does not depend on the mixing ratio of MES to AET in the bathing ethanol solution used for preparing SAMs, chi(soln)MES, over the wide range of chi(soln)MES between 0.01 and 0.95. X-ray photoelectron spectroscopy confirms that at least 80% of AET molecules adsorbed are protonated in this range of chi(soln)MES, indicating that the electrostatic interaction between positively charged AET and negatively charged MES is responsible to the observed nonideality. Correspondingly, there appears only one cathodic peak in a linear-sweep voltammogram of the reductive desorption of the SAM, having a narrow full width at half-maximum of about 20 mV. This suggests the presence of strong lateral attractive interaction between the adsorbed thiolates.     

Nanotribological properties of alkanephosphonic acid self-assembled monolayers on aluminum oxide: effects of fluorination and substrate crystallinity

Two phosphonic acid (PA) self-assembled monolayers (SAMs) are studied on three aluminum oxide surfaces: the C and R crystallographic planes of single crystal alpha-alumina (sapphire) and an amorphous vapor-deposited alumina thin film. SAMs are either fully hydrogenated CH3(CH2)17PO3H2 or semifluorinated CF3(CF2)7(CH2)11PO3H2. Atomic force microscope (AFM) topographic imaging reveals that the deposited films are homogeneous, atomically smooth, and stable for months in the laboratory environment. Static and advancing contact angle measurements agree with previous work on identical or similar films, but receding measurements suggest reduced coverage here. To enable reproducible nanotribology measurements with the AFM, a scanning protocol is developed that leads to a stable configuration of the silicon tip. Adhesion for the semifluorinated films is either comparable to or lower than that for the hydrogenated films, with a dependence on contact history observed. Friction between each film and the tips depends strongly upon the type of molecule, with the fluorinated species exhibiting substantially higher friction. Subtle but reproducible differences in friction are observed for a given SAM depending on the substrate, revealing differences in packing density for the SAMs on the different substrates. Friction is seen to increase linearly with load, a consequence of the tip's penetration into the monolayer.     

Designing highly specific biosensing surfaces using aptamer monolayers on gold

To build highly specific surfaces using aptamer affinity reagents, the effects of linker and coadsorbents were investigated for maximizing target binding and specificity for aptamer-based self-assembled monolayers (SAMs) supported on gold. An aptamer that binds the protein thrombin was utilized as a model system to compare different mixed monolayer systems toward maximizing binding and selectivity to the immobilized aptamer. Important factors used to optimize binding characteristics of thrombin to the aptamer-based monolayer films include changes in design elements of the linker and different coadsorbent thiols. Binding events measured by surface plasmon resonance (SPR) and ellipsometry showed that the binding performance of the aptamer SAMs depends principally on the linker and to a lesser extent on the coadsorbent. SAMs formed with HS-(CH2)6-OP(O)2O-(CH2CH2O)6-TTTTT-aptamer exhibited a 4-fold increase in binding capacity versus SAMs made using HS-(CH2)6-TTTTT-aptamer. Furthermore, SAMs made using HS-(CH2)6-OP(O)2O-(CH2CH2O)6-TTTTT-aptamer showed nearly complete specificity for thrombin versus bovine serum albumin (BSA, less than 2% bound), while a SAM incorporating a random DNA fragment (HS-(CH2)6-OP(O)2O-(CH2CH2O)6-TTTTT-RANDOM) showed little binding of thrombin. Irrespective of the aptamer-linker system, use of HS-(CH2)11(OCH2CH2)3OH, referred to as EG(3), as a coadsorbent enhanced binding of thrombin by approximately 2.5-fold compared to that of HS-(CH2)6-OH (mercaptohexanol, MCH).     

The reaction of tetrakis(dimethylamido)titanium with self-assembled alkyltrichlorosilane monolayers possessing -OH, -NH2, and -CH3 terminal groups

The reactions of tetrakis(dimethylamido)titanium, Ti[N(CH(3))(2)](4), with alkyltrichlorosilane self-assembled monolayers (SAMs) terminated by -OH, -NH(2), and -CH(3) groups have been investigated with X-ray photoelectron spectroscopy (XPS). For comparison, a chemically oxidized Si surface, which serves as the starting point for formation of the SAMs, has also been investigated. In this work, we examined the kinetics of adsorption, the spatial extent, and stoichiometry of the reaction. Chemically oxidized Si has been found to be the most reactive surface examined here, followed by the -OH, -NH(2), and -CH(3) terminated SAMs, in that order. On all surfaces, the reaction of Ti[N(CH(3))(2)](4) was relatively facile, as evidenced by a rather weak dependence of the initial reaction probability on substrate temperature (T(s) = -50 to 110 degrees C), and adsorption could be described by first-order Langmuirian kinetics. The use of angle-resolved XPS demonstrated clearly that the anomalous reactivity of the -CH(3) terminated SAM could be attributed to reaction of Ti[N(CH(3))(2)](4) at the SAM/SiO(2) interface. Reaction on the -NH(2) terminated SAM proved to be the "cleanest", where essentially all of the reactivity could be associated with the terminal amine group. In this case, we found that approximately one Ti[N(CH(3))(2)](4) adsorbed per two SAM molecules. On all surfaces, there was significant loss of the N(CH(3))(2) ligand, particularly at high substrate temperatures, T(s) = 110 degrees C. These results show for the first time that it is possible to attach a transition metal coordination complex from the vapor phase to a surface with an appropriately functionalized self-assembled monolayer.     

Dynamics of the interaction of vapor-deposited copper with alkanethiolate monolayers: bond insertion, complexation, and penetration pathways

We have investigated the interaction of vapor-deposited copper with -CH3, -OH, -OCH3, -COOH, and -CO2CH3 terminated alkanethiolate self-assembled monolayers (SAMs) adsorbed on polycrystalline Au using time-of-flight secondary ion mass spectrometry and density functional theory calculations. For -OH, -COOH, and -CO2CH3 terminated SAMs measurements indicate that for all copper coverages there is a competition between Cu atom bond insertion into C-O bonds, stabilization at the SAM/vacuum interface, and penetration to the Au/S interface. In contrast, on a -OCH3 terminated SAM Cu only weakly interacts with the methoxy group and penetrates to the Au substrate, while for a -CH3 terminated SAM deposited copper only penetrates to the Au/S interface. The insertion of copper into C-O terminal group bonds is an activated process. We estimate that the barriers for Cu insertion are 55 +/- 5 kJ mol(-1) for the ester, 50 +/- 5 kJ mol(-1) for the acid, and 55 +/- 5 kJ mol(-1) for the hydroxyl terminated SAMs. The activation barrier for the copper insertion is much higher for the -OCH3 SAM. Copper atoms with energies lower than the activation barrier partition between complexation (weak interaction) with the terminal groups and penetration through the monolayer to the Au/S interface. Weakly stabilized copper atoms at the SAM/vacuum interface slowly penetrate through the monolayer. In contrast to the case of Al deposition, C-O bond insertion is favored over C=O, C-H, and C-C bond insertion.     

In vitro stability study of organosilane self-assemble monolayers and multilayers

The stability of self-assembled monolayers (SAMs) and multilayers formed on silicon surface by amino-terminated silanes and SAMs formed by alkyl and glycidyl terminated silanes were investigated in vitro with saline solution at 37 degrees C for up to 10 days. FTIR and XPS results indicated that amino-terminated SAMs and multilayers are very unstable if the alkyl chain is short ((CH2)3), while stable if the alkyl chain is long ((CH2)11). On the other hand, alkyl-terminated SAMs are very stable regardless of the alkyl chain length, and glycidyl terminated SAM retained approximately 77% of the organosilane molecules after 10 days. Hydrogen bonding between the organosilane monomer and silicon surface and among the organosilane monomers is believed to contribute to the instability of the SAM and multilayer formed by amino-terminated silane with a short alkyl chain ((CH2)3). Therefore, the widely used (3-aminopropyl) trimethoxysilane (APTMS) SAM and multilayer may not be suitable for implantable biomedical applications.     

Electron transport through thin organic films in metal--insulator--metal junctions based on self-assembled monolayers.

This paper describes an experimentally simple system for measuring rates of electron transport across organic thin films having a range of molecular structures. The system uses a metal--insulator--metal junction based on self-assembled monolayers (SAMs); it is particularly easy to assemble. The junction consists of a SAM supported on a silver film (Ag-SAM(1)) in contact with a second SAM supported on the surface of a drop of mercury (Hg-SAM(2))--that is, a Ag-SAM(1)SAM(2)-Hg junction. SAM(1) and SAM(2) can be derived from the same or different thiols. The current that flowed across junctions with SAMs of aliphatic thiols or aromatic thiols on Ag and a SAM of hexadecane thiol on Hg depended both on the molecular structure and on the thickness of the SAM on Ag: the current density at a bias of 0.5 V ranged from 2 x 10(-10) A/cm(2) for HS(CH(2))(15)CH(3) on Ag to 1 x 10(-6) A/cm(2) for HS(CH(2))(7)CH(3) on Ag, and from 3 x 10(-6) A/cm(2) for HS(Ph)(3)H (Ph = 1,4-C(6)H(4)) on Ag to 7 x 10(-4) A/cm(2) for HSPhH on Ag. The current density increased roughly linearly with the area of contact between SAM(1) and SAM(2), and it was not different between Ag films that were 100 or 200 nm thick. The current--voltage curves were symmetrical around V = 0. The current density decreased with increasing distance between the electrodes according to the relation I = I(0)e(-beta d(Ag,Hg)), where d(Ag,Hg) is the distance between the electrodes, and beta is the structure-dependent attenuation factor for the molecules making up SAM(1). At an applied potential of 0.5 V, beta was 0.87 +/- 0.1 A(-1) for alkanethiols, 0.61 +/- 0.1 A(-1) for oligophenylene thiols, and 0.67 +/- 0.1 A(-1) for benzylic derivatives of oligophenylene thiols. The values of beta did not depend significantly on applied potential over the range of 0.1 to 1 V. These junctions provide a test bed with which to screen the intrinsic electrical properties of SAMs made up of molecules with different structures; information obtained using these junctions will be useful in correlating molecular structure and rates of electron transport.     

Rational aspect ratio and suitable antibody coverage of gold nanorod for ultra-sensitive detection of a cancer biomarker

We report a simple, ultra-sensitive, and straightforward method for non-labeling detection of a cancer biomarker, using Rayleigh light scattering spectroscopy of the individual nanosensor based on antibody-antigen recognition and localized surface plasmon resonance (LSPR) λ(max) shifts. By experimentally measuring the refractive index sensitivity of Au nanorods, the Au nanorod with an aspect ratio of ~3.5 was proven optimal for the LSPR sensing. To reduce the steric hindrance effect as well as to immobilize a large amount of ligand on the nanoparticle surface, various mixtures containing different molar ratios of HS(CH(2))(11)(OCH(2)CH(2))(6)OCH(2)COOH and HS(CH(2))(11)(OCH(2)CH(2))(3)OH were applied to form different self-assembled monolayer surfaces. The results showed that the best molar ratio for antibody conjugation was 1 : 10. When using individual Au nanorod sensors for the detection of prostate specific antigen (PSA), the lowest concentration recorded was ~1 aM (~6 × 10(5) molecules), corresponding to LSPR λ(max) shifts of ~4.2 nm. These results indicate that sensor miniaturization down to the nanoscale level, the reduction of steric hindrance, and optimization of size, shape, and aspect ratio of nanorods have led to a significant improvement in the detection limit of sensors.     

Improved method for the preparation of carboxylic acid and amine terminated self-assembled monolayers of alkanethiolates

We present an improved method to prepare carboxylic acid (COOH) and amine (NH2) terminated self-assembled monolayers (SAMs) of alkanethiolates. In this method, a small amount of CF3COOH (for COOH-SAM) or N(CH2CH3)3 (for NH2-SAM) is added into the ethanolic solution of alkanethiols during SAM formation. The freshly formed COOH- and NH2-SAMs are then rinsed with an ethanolic solution of NH4OH or CH3COOH, respectively. Both SAMs prepared with the improved method show better quality in terms of surface chemical composition, roughness, and wettability as measured by X-ray photoelectron spectroscopy, atomic force microscopy, and contact angle, respectively. The formation of better SAMs can be attributed to the disruption of interplane hydrogen bonds.     

In-situ characterization of self-assembled monolayers of water-soluble oligo(ethylene oxide) compounds

In-situ spectroscopic ellipsometry (SE) was utilized to examine the formation of the self-assembled monolayers (SAMs) of the water-soluble oligo(ethylene oxide) [OEO] disulfide [S(CH(2)CH(2)O)(6)CH(3)](2) {[S(EO)(6)](2)} and two analogous thiols - HS(CH(2)CH(2)O)(6)CH(3) {(EO)(6)} and HS(CH(2))(3)O(CH(2)CH(2)O)(5)CH(3) {C(3)(EO)(5)} - on Au from aqueous solutions. Kinetic data for all compounds follow simple Langmuirian models with the disulfide reaching a self-limiting final state (d=1.2nm) more rapidly than the full coverage final states of the thiol analogs (d=2.0nm). The in-situ ellipsometric thicknesses of all compounds were found to be nearly identical to earlier ex-situ ellipsometric measurements suggesting similar surface coverages and structural models in air and under water. Exposure to bovine serum albumin (BSA) shows the self-limiting (d=1.2nm) [S(EO)(6)](2) SAMs to be the most highly protein resistant surfaces relative to bare Au and completely-formed SAMs of the two analogous thiols and octadecanethiol (ODT). When challenged with up to near physiological levels of BSA (2.5mg/mL), protein adsorption on the final state [S(EO)(6)](2) SAM was only 3% of that which adsorbed to the bare Au and ODT SAMs.     

Protein interactions with model chromatographic stationary phases constructed using self-assembled monolayers

Model surfaces representative of chromatographic stationary phases were developed by immobilising an homologous series (C2-C18) of n-alkylthiols, mixed monolayers of C4/C18 and thioalkanes with alcohol, carboxylic acid, amino and sulphonic acid terminal groups onto a flat, silver-coated glass surface using self-assembled monolayer (SAM) chemistry. The processes of adsorption and desorption of serum albumins onto the monolayer surfaces was monitored in real-time using surface plasmon resonance (SPR). Alkyl-terminated SAMs all showed a strong adsorption of bovine serum albumin which was largely independent of alkyl chain length, the ratio of mixed C4/C18 SAMs or the solution pH/ionic strength. The adsorption of human serum albumin to carboxylic and amine terminated SAMs was shown to be predominantly via non-electrostatic interactions (hydrophobic or hydrogen bonding). However, sulphonic acid terminated SAMs showed almost exclusively electrostatic interactions with human serum albumin. This preliminary work using self-assembled monolayer chemistry confirms the usefulness of well characterised SAMs surfaces for investigating protein adsorption and desorption onto/from model chromatography surfaces and gives some guidance for selecting appropriate functionalities to develop better surfaces for chromatography and electrophoresis.