Orientation Of Monolayers Research Articles

Mapping single macromolecule chains using the colloid deposition method: PDADMAC on mica

Monolayers of the cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) on mica were thoroughly characterized using the streaming potential and the colloid deposition methods. Initially, the stability of the monolayers was determined by performing desorption experiments carried out under diffusion-controlled regime. It was shown that the desorption of the polyelectrolyte at the ionic strength range 0.01–0.15M is negligible over the time of 20h. The structure of PDADMAC monolayers and orientation of molecules were evaluated using the colloid deposition measurements involving negatively charged polystyrene latex microspheres, 820nm in diameter. The functional relationships between the polyelectrolyte coverage and latex coverage deposited within 20h were acquired by direct optical microscope. In this way the influence of ionic strength varied in the range 0.15–0.01M on the molecule orientation in monolayers was determined. It was shown that for ionic strength of 0.15M nearly one to one mapping of polyelectrolyte chains by colloid particles can be achieved for PDADMAC coverage below 0.1%. In this way, because of a considerable surface area ratio between the macromolecule and the colloid particle, an enhancement factor of 103 can be attained. This behavior was quantitatively interpreted in terms of the random site adsorption model whereas the classical mean-field theory proved inadequate. On the other hand, for lower ionic strength, it was confirmed that an irreversible immobilization of latex particles can only occur at a few closely spaced PDADMAC chains. It was shown that these experimental results were consistent with the side-on adsorption mechanisms of PDADMAC at mica for the above ionic strength.

Effect of pH on the control of molecular orientation in monolayer of bent-core liquid crystal materials by Langmuir–Blodgett method

Control of molecular orientation at the substrate surface is significant to understand the surface science. Langmuir films of bent-core liquid crystals having alkyl chains at both ends were deposited on silicon substrate. Studies were carried out on air–water interface by changing pH of the subphase. On compression, molecules were arranged in stacks at high pH where as uniform monolayer was formed at lower pH. Limiting area increased at low pH, which resulted in the formation of monolayer after attaining a sustainable surface pressure. Langmuir films were transferred to silicon substrate, and atomic force microscopy images showed appropriate height profiles.

Adsorption from n-heptane/benzene liquid mixture on acid leached bentonite powders

In this study, adsorption excess isotherms of n-heptane/benzene liquid mixture on hydrochloric acid leached bentonite powders were determined. Adsorptions were conducted at 25°C for 48h. Experimental results were evaluated with both Schay–Nagy (SN) and Everett (E) methods. Specific surface areas (SSN and SE) of the powders were calculated regarding monolayer adsorption capacity of the preferentially adsorbed benzene. Adsorption equilibrium constants (K≫1) were obtained by the E-method. The SE and SSN values are closed to each other. SE-values were found much lower than the corresponding Brunauer, Emmett and Teller (BET)-values. This difference was discussed with respect to the interaction of adsorbed molecules with solid surface, their collision diameter, molar cross sectional surface area and orientation in dense monolayer. Even the maximum for the SE was not associated with the maxima for K and nanopore volume (V), their values changed approximately parallel to each other with respect to the HCl% by the leaching.

Formation and stability of organic acid monolayers on magnesium alloy AZ31: The role of alkyl chain length and head group chemistry

Magnesium wrought alloy AZ31 has a 30% lower density than aluminum alloys and provides the opportunity to reduce vehicle weight and hence to reduce fuel consumption. Today, the use in industrial applications is limited due to low corrosion resistance. Carboxylic and phosphonic acids were investigated as promising alternatives for corrosion protection on AZ31 magnesium wrought alloy. Adsorption and orientation of organic monolayers were studied as a function of aliphatic chain lengths and head groups. As final result, the octadecylphosphonic acid led to a measureable lowering of the corrosion current density and inhibited the growth of the oxide film under humid conditions.

Orientation of Phenylphosphonic Acid Self-Assembled Monolayers on a Transparent Conductive Oxide: A Combined NEXAFS, PM-IRRAS, and DFT Study

Self-assembled monolayers (SAMs) of dipolar phosphonic acids can tailor the interface between organic semiconductors and transparent conductive oxides. When used in optoelectronic devices such as organic light emitting diodes and solar cells, these SAMs can increase current density and photovoltaic performance. The molecular ordering and conformation adopted by the SAMs determine properties such as work function and wettability at these critical interfaces. We combine angle-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) to determine the molecular orientations of a model phenylphosphonic acid on indium zinc oxide, and correlate the resulting values with density functional theory (DFT). We find that the SAMs are surprisingly well-oriented, with the phenyl ring adopting a well-defined tilt angle of 12-16° from the surface normal. We find quantitative agreement between the two experimental techniques and density functional theory calculations. These results not only provide a detailed picture of the molecular structure of a technologically important class of SAMs, but also resolve a long-standing ambiguity regarding the vibrational-mode assignments for phosphonic acids on oxide surfaces, thus improving the utility of PM-IRRAS for future studies.

Analysis of molecular monolayers adsorbed on metal surfaces by glow discharge optical emission spectrometry

The pioneering study of Shimizu et al. (J. Anal. At. Spectrom., 2004, 19, 692) on the examination of adsorbed organic molecules on a copper substrate by radio frequency glow discharge optical emission spectrometry (rf-GDOES) displayed the potential of GDOES for determination of the orientations of molecular monolayers. Here, the study has been extended to the examination of thiourea adsorbed on silver, gold and copper surfaces and metal-centred molecular wires (MCMWs) of 4–6 nm length, with cobalt atoms in the middle of the chain adsorbed on a gold surface. According to established data, these molecules are adsorbed onto a metal surface through a sulphur atom. Depth profiling of thiourea adsorbed on the copper surface confirmed the results of Shimizu et al., with a nitrogen peak followed by a sulphur peak in the depth profile revealed with sputtering time. However, in the case of silver and gold substrates, the positions of the sulphur and nitrogen peaks in the depth profiles were not as predicted from the orientation of the thiourea molecule, i.e. the nitrogen peak followed the sulphur peak with sputtering time or the peaks overlapped. In the depth profiles of the adsorbed MCMWs, the sulphur peak appeared prior to the cobalt peak with sputtering time. Further, the time required for sputtering of thiourea and the wires are comparable, whereas the lengths of thiourea and the wire molecules differ by more than one order of magnitude. Thus, in this case, no correlation between the orientation of the molecules and the peak sequence in the depth profiles has been observed.

Poly (oxypropylene)-amidoamine modified bentonite as potential shale inhibitor in water-based drilling fluids

A series of poly(oxypropylene)-amidoamine (POAA) compounds as potential shale inhibitors were synthesized by condensation of low molar mass polyoxypropylene diamine POP230 with diacids. The synthesized polymer was characterized by Fourier transform infrared spectroscopy (FT-IR) and mass spectrum (MS) analysis. The interaction between the POAA compounds and purified bentonite was investigated via FT-IR, X-ray diffraction (XRD), electrophoretic mobility (EM) measurement, thermogravimetric analysis (TGA), water adsorption test, and scanning electron microscopy (SEM). The POAA compounds were intercalated by the montmorillonite (Mt) with monolayer orientation. The protonated ammonium ions neutralized the negatively charged sites and decreased the electrophoretic mobility. Hydrogen bonds were formed between amide and siloxane groups. The intercalation reduced the water content of the Mt and rendered the clay mineral surface more hydrophobic. The inhibitive properties of the modified Mt were evaluated by inhibition and cuttings hot-rolling dispersion tests. The POAA-Mt exhibited superior shale hydration and dispersion inhibition capacity compared to conventional inhibitors.

Investigations on Microstructural and Layer Disorder Parameters of Na-Montmorillonite-Glycine Intercalation Compounds

Glycine-Montmorillonite (Gly-MMT) composite has been synthesized through intercalation process using Na-Montmorillonite (Na- MMT) and glycine ethylester hydrochloride. Gly-MMT was employed for the synthesis of dipeptide (Gly-Gly-MMT). Microstructural parameters such as crystallite size, r.m.s. strain (<e2>1/2) and layer disorder parameters such as variation of interlayer spacing (g) and proportion of planes affected by such defects (?) of the samples have been calculated by X-ray line profile analysis. In comparison to Na-MMT the basal spacings (d001) of Gly-MMT and Gly-Gly-MMT were reduced by 2.4Å and 1.8Å respectively. The value of d001 of Gly-Gly-MMT (13.3 Å) suggests the monolayer orientation of dipeptide into interlayer spaces. It is also suggested that more homogeneity in the stacking of silicate layers is attained in Gly-Gly-MMT due to the increased chain length of the dipeptide and orientation in monolayer style.DOI: http://dx.doi.org/10.3329/dujs.v60i1.10331Dhaka Univ. J. Sci. 60(1): 25-29, 2012 (January)

Towards room temperature ionic liquid crystals: linear versus bent imidazolium phenylpyrimidines

The synthesis and the mesomorphic properties of novel imidazolium salts with mesogenic 2-phenylpyrimidine or 2-alkylpyrimidinecarboxylic acid central cores are reported. The mesogenic units are connected to the imidazolium head groups via an alkoxy spacer. In order to adjust the mesomorphic properties the length of the alkoxy spacer and the terminal alkyl group, the counter ion, the substitution pattern of the imidazolium head group and the molecular geometry (linear vs. bent) are varied and the corresponding compounds were investigated in detail using differential scanning calorimetry (DSC), polarized optical microscopy (POM) and X-ray scattering (WAXS, SAXS). Whereas SmA phases with monolayer orientation were observed for imidazolium salts with short N-substituents (R = CH3, C4H9) at the imidazolium head group, the corresponding derivatives with longer N-substituents (R = C12H25, C12H25OC6H4) displayed SmA phases with bilayer orientation irrespective of a linear or bent geometry. For two derivatives, p-5(10,8) and p-5(12,8), a SmC phase was observed. Indeed, bending of the mesogenic core led to a shift of the mesophases towards lower temperatures. Several of the meta-2-phenylpyrimidine derivatives as well as 2-pyrimidine carboxylates displayed melting points below 50 °C. For 2-pyrimidine carboxylates replacement of a bromide anion by triflate resulted in a further decrease of the melting transition close to ambient temperature.

Nucleoside-Assisted Self-Assembly of Oligo(p-phenylenevinylene)s at Liquid/Solid Interface: Chirality and Nanostructures

The formation of DNA nucleoside-assisted π-conjugated nanostructures was studied by means of scanning tunneling microscopy (STM) and force field simulations. Upon adsorption of the achiral oligo(p-phenylenevinylene) (OPV) derivative at the liquid/solid interface, racemic conglomerates with mirror related rosettes are formed. Addition of the DNA nucleosides D- and L-thymidine, which act as "chiral handles", has a major effect on the supramolecular structure and the expression of chirality of the achiral OPV molecules. The influence of these "chiral handles" on the expression of chirality is probed at two levels: monolayer symmetry and monolayer orientation with respect to the substrate. This was further explored by tuning the molar ratio of the building blocks. Molecular modeling simulations give an atomistic insight into the monolayer construction, as well as the energetics governing the assembly. Thymidine is able to direct the chirality and the pattern of OPV molecules on the surface, creating chiral lamellae of π-conjugated dimers.

Improved properties of highly oriented graphene/polymer nanocomposites

AbstractA kind of molecular‐level dispersed and highly oriented graphene monolayer nanocomposite film was successfully obtained by in situ reduction of phenyl isocyanate functionalized graphite oxide (RPIGO) in N,N‐dimethylformamide in the presence of polystyrene (PS). Atomic force microscopy and transmission electron microscopy results show that the RPIGO monolayers were not only homogeneously intercalated into the PS matrix but also arranged parallel to the surface of the nanocomposite films. Because of the efficient interaction between the graphene monolayers and PS matrix, the mechanical properties of the graphene‐based nanocomposite films improved significantly. Compared with the pure PS film, a 28.4% increase in the Young's modulus and a 27.8% improvement in the tensile strength of the RPIGO–PS nanocomposites films were obtained with the addition of only 0.5 wt % graphite oxide. The glass‐transition temperature and onset degradation temperature of PS also increased from 96.6 and 427°C to 103.2 and 439°C, respectively. The improvement of the properties was mainly due to the large lateral thickness ratio and the high orientation of graphene monolayers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Comparison of a Fluorinated Aryl Thiol Self-Assembled Monolayer with Its Hydrogenated Counterpart on Polycrystalline Ag Substrates

The effects of perfluorination of aryl thiols on surface coverage, surface electronic properties, and molecular orientation of self-assembled monolayers of thiophenol (TP) and pentafluorothiophenol (F(5)TP) on polycrystalline Ag were evaluated using linear sweep voltammetry, ultraviolet photoelectron spectroscopy (UPS), and surface Raman spectroscopy, respectively. Electrochemical reductive desorption by linear sweep voltammetry indicates a surface coverage for the TP monolayer of (5.07 +/- 1.29) x 10(-10) mol/cm(2), equating to a molecular area of 32.8 +/- 8.3 A(2), and a surface coverage for the F(5)TP monolayer of (1.95 +/- 0.59) x 10(-10) mol/cm(2), equating to an area of 85.2 +/- 25.8 A(2)/molecule. TP-modified Ag exhibits a change in work function (DeltaPhi) of -0.64 eV relative to bare Ag, whereas F(5)TP-modified Ag exhibits a DeltaPhi of +0.54 eV relative to bare Ag. Quantitative analysis of the UPS and reductive desorption results yields molecular pictures of the proposed interfaces with TP molecules tilted <20 degrees from the surface normal in a herringbone pattern spaced 6.4 A apart and F(5)TP molecules in a more disordered arrangement tilted 67 degrees from the surface normal with an intermolecular distance of 10.4 A. Qualitative surface Raman spectroscopic analysis of in-plane and out-of-plane modes for these systems confirms that TP molecules are oriented more vertical than F(5)TP molecules in these monolayers.

Electron transfer kinetics and morphology of cytochrome c at the biomimetic phospholipid layers

Abstract Electrochemistry of cytochrome c (cyt c) at biomimetic phospholipid layers was studied in a phosphate buffer solution, which were formed with dilauroyl phosphatidic acid (DLPA, C12:0), dipalmitoyl phosphatidic acid (DPPA, C16:0), distearoyl phosphatidic acid (DSPA, C18:0), and palmitoyl–oleoyl phosphatidic acid (POPA, C16:0–18:1). The lipid-layers formed firstly at the air/water interface were immediately transferred onto the electrode surface using the Langmuir–Blodgett (LB) technique. The electrochemical properties of cyt c at the lipid covered electrodes depended on the orientation, number of layers of phospholipids, tail (or head) group down, and vice versa. Atomic force microscopy (AFM) images of cyt c adsorbed on the POPA monolayer (showing the head group diameter of POPA to be ca. 0.7 nm) formed on highly oriented pyrolytic graphite (HOPG) displayed uniform surface morphology of lipid layer and clumps of aggregated cyt c molecules with a minimum size corresponding to four cyt c molecules. The heterogeneous electron transfer rate constants, k0 values, of cyt c were determined to be 1.02 × 10−3, 0.98 × 10−3, and 0.67 × 10−3 cm/s for the lipid monolayer in the tail down orientation (X-type) of POPA, DLPA, and DPPA, and 0.67 × 10−3 and 0.50 × 10−3 cm/s for the head down orientation (Z-type) of POPA and DLPA monolayers, respectively.

Monolayer Orientation of ω-Substituted Amide-Bridged Alkanethiols on Gold

A new set of aryl-substituted amides of 16-mercaptohexadecanoic acid (R = 4-OCH3; 3,5-di-OCH3) are synthesized using a simple and general procedure. Self-assembled monolayers of these molecules on Au(111) are studied by infrared and visible ellipsometry and contact angle measurements. Model calculations are employed to determine the molecular tilt angle. The SAM methylene chains exist in prevailing all-trans conformation and the tilt of the CCC plane is decreased by approximately 15° in comparison with the correspondent value for n-alkanethiols. Strong hydrogen bonds between the amide proton and the carbonyl oxygen are detected with C═O and N−H dipoles oriented parallel to the gold surface. The wetting of the outermost film surface reveals predominantly OCH3 groups exposed.

Comparative Study of Tetrahydrothiophene and Thiophene Self Assembled Monolayers on Au(111): Structure and Molecular Orientation

Surface structure and molecular orientation of self-assembled monolayers (SAMs) formed by the spontaneous adsorption of tetrahydrothiophene (THT) and thiophene (TP) on Au(111) were investigated by means of scanning tunneling microscopy (STM) and carbon K-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy. STM imaging revealed that THT SAMs have a commensurate (3 <TEX>${\times}\;2\sqrt[]{3}$</TEX>) structure containing structural defects in ordered domains, whereas TP SAMs are composed of randomly adsorbed domains and paired molecular row domains that can be described as an incommensurate packing structure. The NEXAFS spectroscopy study showed that the average tilt angle of the aliphatic THT ring and <TEX>$\pi$</TEX>-conjugated TP ring in the SAMs were calculated to be about <TEX>$30^o\;and\;40^o$</TEX>, respectively, from the surface normal. It was also observed that the <TEX>$\pi$</TEX>* transition peak in the NEXAFS spectrum of the TP SAMs is very weak, suggesting that a strong interaction between <TEX>$\pi$</TEX>-electrons and the Au surface arises during the self-assembly of TP molecules. In this study, we have clearly demonstrated that the surface structure and adsorption orientation of organic SAMs on Au(111) are strongly influenced by whether the cyclic ring is saturated or unsaturated.

Determining orientational structure of diamondoid thiols attached to silver using near-edge X-ray absorption fine structure spectroscopy

Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) is a powerful tool for determination of molecular orientation in self-assembled monolayers and other surface-attached molecules. A general framework for using NEXAFS to simultaneously determine molecular tilt and twist of rigid molecules attached to surfaces is presented. This framework is applied to self-assembled monolayers of higher diamondoids, hydrocarbon molecules with cubic-diamond-cage structures. Diamondoid monolayers chemisorbed on metal substrates are known to exhibit interesting electronic and surface properties. This work compares molecular orientation in monolayers prepared on silver substrates using two different thiol positional isomers of [121]tetramantane, and thiols derived from two different pentamantane structural isomers, [1212]pentamantane and [1(2,3)4]pentamantane. The observed differences in monolayer structure demonstrate the utility and limitations of NEXAFS spectroscopy and the framework. The results also demonstrate the ability to control diamondoid assembly, in particular the molecular orientational structure, providing a flexible platform for the modification of surface properties with this exciting new class of nanodiamond materials.

Interaction of the Protein Retinitis Pigmentosa 2 (RP2) with Langmuir Phospholipid Monolayers

A severe form of retinitis pigmentosa is linked to mutations of the 350 residues protein RP2 (retinitis pigmentosa 2). This protein contains a α/β C-terminal domain, a highly hydrophobic β-helix and two acylation sites at the N-terminal. It localizes predominantly to the membrane. However, the parameters responsible for the modulation of RP2 binding to membranes are still largely unknown. The objectives of this research work were to characterize the membrane binding properties of RP2 using Langmuir monolayers. The complete sequence of RP2 was expressed and high purity was achieved. RP2 was injected into the subphase underneath phospholipid monolayers bearing different fatty acyl chains (length and unsaturation) and polar headgroups. RP2 binding was monitored by surface pressure measurements. The injection of RP2 underneath phospholipid monolayers led to an increase in surface pressure which indicates its membrane binding. The surface pressure data demonstrate that the adsorption kinetics of RP2 is independent of pH but is strongly affected by the ionic strength of the subphase as well as by the type of phospholipid fatty acyl chain (length and unsaturation) and headgroup. For example, on the basis of its maximum insertion pressure, RP2 shows a preferential binding onto saturated phospholipid monolayers which is consistent with its postulated localization to rafts. This interaction has been further studied by infrared sprectoscopy. In solution, the amide I band is centered at 1630 cm−1, indicating the presence of the β-helix. In contrast, when injected into the subphase in the absence and presence of a phospholipid monolayer, the amide I band is shifted to longer wavenumbers with components at 1640 and 1655 cm−1. These data thus suggest that RP2 has a preferential orientation in monolayers where the α/β C-terminal domain is oriented towards the monolayer.

Molecular Orientation in Octanedithiol and Hexadecanethiol Monolayers on GaAs and Au Measured by Infrared Spectroscopic Ellipsometry

Infrared spectroscopic ellipsometry was used for determination of molecular orientation and for lateral homogeneity studies of organic monolayers on GaAs and Au, the organic layer being either octanedithiol or hexadecanethiol (HDT). The laterally resolved measurements were performed with the infrared mapping ellipsometer at the synchrotron storage ring BESSY II. The molecular orientation within the monolayers was determined by optical model simulations of the measured ellipsometric spectra. Different tilt angles were obtained for the monolayers of HDT and octanedithiol on GaAs: 19 degrees and >30 degrees , respectively. The tilt angle of the methylene chains for HDT on Au substrate (22 degrees ) is similar to the 19 degrees tilt which was obtained for the HDT monolayers on GaAs, thus suggesting similar molecular ordering of the thiolates on both substrates.

Sum-frequency-generation spectroscopy of DNA films in air and aqueous environments

Understanding the organization and orientation of surface-immobilized single stranded DNA (ssDNA) in aqueous environments is essential for optimizing and further developing the technology based on oligonucleotide binding. Here the authors demonstrate how sum-frequency-generation (SFG) spectroscopy can be used to compare the structure and orientation of model monolayers of ssDNA on gold in air, D(2)O, and phosphate buffered saline (PBS) solution. Films of adenine and thymine homo-oligonucleotides showed significant conformational changes in air versus aqueous environments in the CH stretching region. The thymine films showed changes between D(2)O and PBS solution, whereas the SFG spectra of adenine films under these conditions were largely similar, suggesting that the thymine films undergo greater conformational changes than the adenine films. Examination of thymine films in the amide I vibrational region revealed that molecules in films of nonthiolated DNA were lying down on the gold surface whereas molecules in films of thiol-linked DNA were arranged in a brushlike structure. Comparison of SFG spectra in the amide I region for thiol-linked DNA films in air and D(2)O also revealed substantial conformational changes.

Patchy Particles by Glancing Angle Deposition

The application of glancing angle deposition (GLAD) as a means to produce patchy particles is reported. Shadow effects are caused by neighboring particles within the particle monolayer. The patch geometry is determined by the angle of incidence of the vapor rays and the monolayer orientation. A mathematical model is used to study the patch geometry and to calculate the area of the patch. The smallest patch produced with GLAD is 3.7% of the particle surface.