Characterization Of Self-assembled Monolayers Research Articles

New Approach to Simultaneous In Situ Measurements of the Air/Liquid/Solid Interface Using PM-IRRAS.

Vibrational spectroscopy techniques have evolved to measure gases, liquids, and solids at surfaces and interfaces. In the field of surface-sensitive vibrational spectroscopy, infrared spectroscopy measures the adsorption on surfaces and changes from reactions. Previous polarized modulated-infrared reflection-absorption spectroscopy (PM-IRRAS) measurements at the gas/solid interface were developed to observe catalytic reactions near reaction conditions. Other PM-IRRAS measurements use liquid cells where the sample is submerged and compressed against a prism that has traditionally been used for electrochemical reactions. This article presents a new method that is used to observe in situ adsorption of molecules using PM-IRRAS at the gas/liquid/solid interface. We demonstrate the meniscus method by measuring the adsorption of octadecanethiol on gold surfaces. Characterization of self-assembled monolayers (SAMs), the "gold standard" for PM-IRRAS calibration measurements, was measured in ethanol solutions. The condensed-phase (air/liquid) interface in addition to the liquid/solid interface was measured simultaneously in solution. These are compared with liquid attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy measurements to confirm the presence of the SAM and liquid ethanol. A model of the three-phase system is used to approximate the thickness of the liquid ethanol layer and correlate these values to signal attenuation using PM-IRRAS. This proof-of-concept study enables the measurement of reactions at the gas/liquid/solid interface that could be adapted for other reactions at the electrode and electrolyte interfaces with applications in environmental science and heterogeneous catalysis.

Characterization of Self-Assembled Monolayers on a Ruthenium Surface.

We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on piranha-cleaned and piranha + H2SO4 cleaned substrates were compared to monolayers formed on H-radical-cleaned Ru surfaces. We found that alkanethiols on H-radical-cleaned Ru formed densely packed monolayers that remained stable when kept in a nitrogen atmosphere. X-ray photoelectron spectroscopy (XPS) shows a distinct sulfur peak (BE = 162.3 eV), corresponding to metal–sulfur bonding. When exposed to ambient conditions, the SAM decayed over a period of hours.

Characterizing Self-Assembled Monolayers on Gold Nanoparticles.

A key aspect of nanoscience is to control the assembly of complex materials from a "bottom-up" approach. The self-assembly and self-organization of small ligands at the surface of nanoparticles represent a possible starting route for the preparation of (bio)nanomaterials with precise (bio)physical and (bio)chemical properties. However, surface characterization and elucidation of the structure-properties relationship, essential to envisioning such control, remain challenging and are often poorly investigated. This Topical Review aims to discuss different levels of surface characterization, giving an overview of the experimental and computational approaches that are used to provide insights into the self-assembled monolayer with molecular details. The methods and strategies discussed focus on the characterization of self-assembled monolayers at the gold nanoparticle surface, but most of them could also be applied to other types of nanoparticles.

Characterization of self-assembled monolayers (SAM) of peptide mimotopes of CD20 antigen and their binding with rituximab (R) using Quartz Crystal Microbalance (QCM) Piezo-Immunosensors: A novel technique to study CD20 antigen interaction.

e14004 Background: CD20 antigen is an established target for antibody therapy like R. Understanding interactions of CD20 antigens is important for developing better agents and overcoming resistance. We have developed a new innovative biosensor based quantitative technique to study real time interaction of CD20 antigens with R using QCM Piezo-immunosensor, which can be used to characterize cell surface antigen, study interactions and understand mechanisms of resistance. Methods: Binding of R with SAM of peptide mimotopes of CD20 antigen was systematically characterized. Four peptide mimotopes of CD 20 antigen were selected from literature and redesigned to allow their SAM immobilizations on gold electrodes through a peptide linker with cysteine. The bindings of these peptides with R and control antibodies (Trastuzumab, Bevacizumab) were characterized by Quartz Crystal Microbalance (QCM). Among the four peptide mimotopes initially selected, the peptide designated as CN-14 was the most selective and sensitive for R binding, which was further characterized by ellipsometry, atomic force microscopy and QCM. Results: We have shown a systematic approach for using QCM technique to quantify the apparent binding of CD20 and R. As the GLU residue pKa of CN-14 increased, the affinity of the SAM to Rituximab increased while the selectivity decreased. This was attributed to the weakening of the salt bridge between the CN-14 ARG-10 and GLU-13 at higher pKa values for GLU-13. Conclusions: Interaction of CD20 antigens with antibodies will help physicians to determine the clinical efficacy and resistance mechanisms to antibodies like R. QCM is low cost, highly sensitive, fast, synthetic, assay which could be used as a basis for developing a new generation of affinity-based Immunosensor assays. Our study shows that peptide mimotopes have potential benefit in sensor applications as the peptide-peptide interactions in the SAM could be manipulated by the addition of functional groups to the peptide to influence binding of the target protein as well as for surface immobilization via SAM.

Self-assembled monolayers of alkyl-thiols on InAs: A Kelvin probe force microscopy study

Abstract We report on the preparation and characterization of self-assembled monolayers from aliphatic thiols with different chain length and termination on InAs (100) planar surfaces. This included as first step the development and investigation of a thorough chemical InAs surface preparation step using a dedicated bromine/NH4OH-based etching process. Ellipsometry, contact angle measurements and atomic force microscopy (AFM) indicated the formation of smooth, surface conforming monolayers. The molecular tilt angles were obtained as 30 ± 10° with respect to the surface normal. Kelvin probe force microscopy (KPFM) measurements in hand with Parameterized Model number 5 (PM5) calculations of the involved molecular dipoles allowed for an estimation of the molecular packing densities on the surface. We obtained values of up to n = 1014 cm− 2 for the SAMs under study. These are close to what is predicted from a simple geometrical model that would calculate a maximum density of about n = 2.7 × 1014 cm− 2. We take this as additional conformation of the substrate smoothness and quality of our InAs–SAM hybrid layer systems.

Characterization of Self-Assembled Monolayer on Anodized Aluminum by XPS, AFM and Low-Voltage SEM

Organic layers of tetradecylphosphonic acid (TDP) and octadecyltrietoxysilane (OES) are formed on flat anodized aluminum surfaces by a simple immersion process. The organic layers are characterized by dynamic contact angle measurements for water, AFM, low-voltage SEM and angle-resolved XPS. The results indicate that a self-assembled monolayer is formed using TDP, but not for OES. Plasma surface treatment prior to the coating was found to significantly influence the formation of organic layers.

The Unusual Self-Organization of Dialkyldithiophosphinic Acid Self-Assembled Monolayers on Ultrasmooth Gold

We report the formation and characterization of self-assembled monolayers (SAMs) of dialkyldithiophosphinic acid adsorbates [CH3(CH2)n]2P(S)SH (R2DTPA) (n = 5, 9, 11, 13, 15) on ultrasmooth gold substrates prepared by the template stripping method. The SAMs were characterized using X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, contact angle measurements, lateral force microscopy, and electrochemical impedance spectroscopy. The data show these SAMs exhibit an unusual trend in alkyl chain crystallinity; SAMs formed from adsorbates with short alkyl chains (n = 5) are ordered and crystalline, and the alkyl groups become increasingly disordered and liquidlike as the number of methylene units is increased. This trend is the opposite of the typical behavior exhibited by n-alkanethiolate SAMs, in which the alkyl layer becomes more crystalline and ordered as the alkyl chain length is increased. We discuss four factors that operate together to determine how R2DTPA self-organize within SAMs on TS gold: (i) adsorbate-substrate interactions; (ii) gold substrate morphology; (iii) lateral van der Waals interactions between alkyl groups; and (iv) steric demands of the alkyl groups. We also present a model for the structures of these SAMs on the basis of consideration of the data and the structural parameters of a model (n)Bu2DTPA adsorbate. In this model, interdigitation of short alkyl chains stabilizes a trans-extended, crystalline arrangement and produces an ordered alkyl layer. As the alkyl chain length is increased, the increased steric demands of the alkyl groups lead to liquidlike, disorganized alkyl layers.

Characterization of Self-Assembled Monolayer On Anodized Aluminum By XPS, AFM and Low-Voltage SEM

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Formation of Self-Assembled Monolayers with Homogeneously Mixed, Loosely Packed Alkyl Groups Using Unsymmetrical Dialkyldithiophosphinic Acids

We report the formation and characterization of self-assembled monolayers (SAMs) formed from unsymmetrical dialkyldithiophosphinic acid (R(1)R(2)DTPA) adsorbates [CH(3)(CH(2))(n)][CH(3)(CH(2))(15)]P(S)SH (n = 5, 9) on gold substrates. These SAMs were characterized using X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, contact angle goniometry, electrochemical impedance spectroscopy, and atomic force microscopy. Unsymmetrical R(1)R(2)DTPA SAMs contain mixtures of bidentate and monodentate adsorbates, similar to SAMs formed from analogous symmetrical R(2)DTPAs. In unsymmetrical R(1)R(2)DTPA SAMs, however, the short alkyl substituent of the R(1)R(2)DTPA adsorbates enforces spacing between the long hexadecyl substituents, which disrupts van der Waals interactions and causes the hexadecyl groups to be loosely packed and disordered. The structure of the SAM depends on the length of the short alkyl substituent: The hexyl chains in the C(6)C(16)DTPA SAM are not long enough to stabilize the alkyl zone close to the substrate, leading to highly disordered SAMs with a low molecular packing density in which the hexadecyl chains lie down to fill the gaps between adjacent adsorbates. In contrast, the additional van der Waals interactions provided by the decyl chains of the C(10)C(16)DTPA SAM enable dense molecular packing in the alkyl zone close to the substrate. The structure of the SAM consists of a zone close to the substrate composed of a packed alkyl layer, with hexadecyl chains protruding above to form a loosely packed, disordered alkyl layer. Regardless of the structural differences between the C(6)C(16)DTPA and C(10)C(16)DTPA SAMs, both SAMs exhibit homogeneous mixing of the alkyl chains within the SAM, demonstrating that binding two different chains to a single headgroup is an effective method to prevent phase segregation.

Synthesis and Characterization of Self-Assembled Monolayer and Bilayer Carboxyl-Group Functionalized Magnetic Nanoparticles

Magnetic nanoparticles functionalized with carboxyl-group have considerable potential to be used as bio-labels due to their conjugation abilities with proteins. Here, we synthesized the iron oxide nanoparticles functionalized with carboxyl groups through self-assembled monolayer coating using citric acid and self-assembled bilayer coating using fatty acids. Their dimension, hydrodynamic size, surface property, and magnetic behavior were characterized through transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, thermal gravimetric analysis, and vibrating sample magnetometry. We also confirmed the binding ability of these nanoparticles with bovine serum albumin on thin gold film.

Influence of Alkyl Chain Length on the Structure of Dialkyldithiophosphinic Acid Self-Assembled Monolayers on Gold

We report the formation and characterization of self-assembled monolayers (SAMs) based on dialkyldithiophosphinic acid adsorbates {[CH(3)(CH(2))(n)](2)P(S)SH (n = 5, 9, 11, 13, 15)} on gold substrates. SAMs were characterized using X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, contact angle measurements, and electrochemical impedance spectroscopy. Data show that there is a roughly 60:40 mixture of bidentate and monodentate adsorbates in each of these SAMs. The presence of monodentate adsorbates is due to the numerous and deep grain boundaries of the underlying gold substrate, which disrupt chelation. Comparing the characterization data of dialkyldithiophosphinic acid SAMs with those of analogous n-alkanethiolate SAMs shows that both SAMs follow a similar trend: The alkyl chains become increasingly organized and crystalline with increasing alkyl chain length. The alkyl groups of dialkyldithiophosphinic acid SAMs, however, are generally less densely packed than those of n-alkanethiolate SAMs. For short alkyl chains (hexyl, decyl, and dodecyl), the significantly lower packing densities cause the alkyl chains to be liquid-like and disorganized. Long-chain dialkyldithiophosphinic acid SAMs are only slightly less crystalline than analogous n-alkanethiolate SAMs.

Characterization of self-assembled monolayers of porphyrins bearing multiple-thiol and photoelectric response

Abstract Self-assembled monolayers (SAMs) of thiol-derivatized porphyrin molecules on Au substrate have attracted extensively interest for use in sensing, optoelectronic devices and molecular electronics. In this paper, tetra-[ p -(3-mercaptopropyloxy)-phenyl]-porphyrin was synthesized and self-assembled with thiol on Au substrate for porphyrin SAMs (PPS 4 ). The electrochemical results demonstrated that PPS 4 could form excellent SAMs on gold surface. Self-assembled nanojunctions of PPS 4 were fabricated by using gold nanogap electrodes (gap width: ca. 100 nm). With the light on/off, the nanojunctions showed current high/low as nanometer scaled photo switch.

XPS Characterization of Porphyrin Based Self-Assembled Monolayers on Gold

XPS characterization of self-assembled monolayers (SAMs) of tetraphenylporphyrin bearing a rigid tripodal linker by chemisorption of the thiol-derivatized terminal groups on gold substrate is described. The surface structure of the SAMs bearing tripodal linker were analyzed by X-ray photoelectron spectroscopy (XPS), and electrochemical cyclic voltammetry (CV) measurements. XPS confirms the formation of porphyrin SAMs on Au surface and identified bonding configurations of porphyrin molecules in the chemisorption of SAMs. The film thickness values (36 Å) obtained by XPS agree well with the estimated value by assuming the vertical orientation of the molecules on the gold surface. Using the Au4f7/2 as an internal standard, a lower binding energies shift (1.8 eV) of S2p in the SAMs reveals that the porphyrins were chemisorbed onto the surface via sulfurgold bonds. Electrochemical CV measurements suggest near monolayer coverage of the tripodal porphyrins with good stability of the redox SAMs, which have promising application in the development of molecular based electronic device and memory architectures.

The Characterization of Self-Assembled Monolayers on Copper Surfaces by Low-Temperature Plasma Mass Spectrometry

We describe direct analysis of self-assembled monolayers (SAMs) on copper surfaces by low temperature plasma (LTP) mass spectroscopy (MS). Two kinds of SAMs formed from n-dodecylmercaptan (NDM) and l-phenyl-5-mercaptotetrazole (PMTA) were prepared on copper by spontaneous chemisorption. With the LTP probe, desorption and ionization of the SAMs was easily achieved, and the ions produced were introduced into MS for analysis. Characteristic fragment ions from NDM SAMs, mainly [M + M - H](+) (M is the NDM molecule) and from PMTA SAMs, mainly [M + H - S](+) (M is the PMTA molecule), were both absent in the MS spectra of neat NDM and PMTA samples. This provided evidence of the formation of SAMs on copper. As a supplementary method, LTP-MS is helpful in obtaining information on the barrier properties of SAMs on copper, such as inhibitor efficiency (IE) and the surface adsorption concentration of corrosive electrolyte (Γ*) surrounding copper. Aiming for an evaluation of the reliability of LTP-MS, a comparative study of our method and the traditional method of cyclic voltammetry (CV) showed a correlation coefficient higher than 0.97. In addition, a rough, simple procedure for imaging of the distribution of the molecules adsorbed on copper surface was presented. The study supplied a rapid and simple method for direct investigation of SAMs on copper.

Self-Assembled Functional Organic Monolayers on Oxide-Free Copper

The preparation and characterization of self-assembled monolayers on copper with n-alkyl and functional thiols was investigated. Well-ordered monolayers were obtained, while the copper remained oxide-free. Direct attachment of N-succinimidyl mercaptoundecanoate (NHS-MUA) onto the copper surface allowed for the successful attachment of biomolecules, such as β-d-glucosamine, the tripeptide glutathione, and biotin. Notably, the copper surfaces remained oxide-free even after two reaction steps. All monolayers were characterized by static water contact angle measurements, X-ray photoelectron spectroscopy, and infrared reflection absorption spectroscopy. In addition, the biotinylated copper surfaces were employed in the immobilization of biomolecules such as streptavidin.

Tailoring self-assembled monolayers at the electrochemical interface

The main focus of this review is to illustrate the amenability of self-assembled monolayers (SAMs) for functionalisation with different receptors, catalytic materials, biomolecules, enzymes, antigen-antibody, etc for various applications. The review discusses initially about the preparation and characterization of SAMs and tailoring of SAMs by incorporation of suitable recognition elements. A description of how the molecular recognition is achieved through forces like electrostatic, covalent and host-guest interactions is included in the review.

Advances in surface plasmon resonance-based high throughput biochips

This article reviews our recent advances in surface plasmon resonance (SPR) based biochips. It includes four issues, which are the preparation and characterization of high quality gold film, the preparation and characterization of self-assembled monolayer (SAM), dynamics of DNA adsorption on SAMs, and SPR-based microscopies. Numerous topics related to SPR, such as, the modeling of SPR by transmission matrix, effective medium theory, applications of SPR in biology, and SPR-based novel microscopies, are discussed. A novel electrochemical technique, which is extremely useful for the preparation and characterization of high quality SAMs, is also discussed.

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.

Characterisation of Self-Assembled Monolayers on Germanium Surfaces via NEXAFS

The formation of self-assembled monolayers (SAMs) by suitable organic molecules with appropriate anchor groups on semiconductor surfaces may be used either to probe both the chemical state and the quality of the surface or to achieve surface passivation. Molecules with thiol anchor groups are able to bond to hydrogen-terminated germanium surfaces (Ge-S bond). We have prepared SAMs of alkylthiols with trifluoroacetate head groups on germanium. The germanium surface prior to and after SAMs formation has been characterised by Near-Edge X-Ray Absorption Fine Structure spectroscopy (NEXAFS) with synchrotron radiation in the PTB laboratory at BESSY II. We succeeded in assigning S-NEXAFS peaks to the Ge-S bond formed during self-assembly and were able to distinguish between different fluorine species via F-NEXAFS.

Preparation and Characterization of Self-Assembled Monolayers on Germanium Surfaces

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