Methyl-terminated Surface Research Articles

First Principles Modelling of Growth of Hybrid Organic-Inorganic Films

Hybrid organic-inorganic materials fabricated with molecular layer deposition (MLD) are a special class of materials that are attracting great interest in many economically and socially relevant technological applications due to their diphasic and tunable organic-inorganic structure. Despite the growing interest in these hybrid materials, knowledge around relevant precursor chemistries and reaction mechanisms, as well as details of many determined experimental results are unknown. Density functional theory (DFT) has proven to be a powerful tool to investigate and understand the atomic level details of the precursor chemistry and address aspects of the MLD experiments.In our work, we use first principles DFT calculations to examine key steps in the mechanism of hybrid film deposition through MLD by modelling precursor-surface and precursor-precursor reactions. We explore the growth mechanism of aluminium and titanium containing hybrid films, namely alucones and titanicones. Both materials are of high interest for passivation layers in batteries. For alucones we investigate in detail the chemistry of the MLD process between the post-trimethylaluminium (TMA) pulse methyl-terminated Al2O3 surface with aromatic compounds with hydroxy and/or amino groups as reactive groups: hydroquinone (HQ), 4-aminophenol (AP) and p-phenylenediamine (PD). Double reactions of HQ, AP and PDA with the Al2O3 surface are explored in detail to assist the interpretation of the experimental findings regarding the differences found for hybrid films grown with aromatic and aliphatic organic precursors. DFT calculations show that in contrast to aliphatic organics, an upright configuration will be present for HQ, AP and PD so that the molecules are self-assembled in an upright configuration, which leads to thicker hybrid films. We predict that aromatic molecules are the best choice for stable hybrid films and their chemistry can be manipulated without degrading stability. [1]We also investigate in detail the chemistry between the most common titanium precursors, namely titanium tetrachloride (TiCl4) and tetrakis(dimethylamido)titanium (Ti(DMA)4), and ethylene glycol (EG) and glycerol (GL) as the organic precursors for the fabrication of titanicone films. We analyse the impact of the substrate on the initial MLD reactions in titanicone film growth using three different surface models: anatase TiO2, rutile TiO2 and Al2O3. This work highlights the role of the phase of TiO2 and Ti-containing precursors in production of titanicone films and provides motivation to develop a new rutile TiO2 based hybrid film suggesting that the desired film growth, flexibility and stability can be achieved. [2][1] A. Muriqi, M. Karppinen and M. Nolan, Role of terminal groups in aromatic molecules on the growth of Al2O3-based hybrid materials, Dalton Transactions, 2021, 50, 17583-17593. doi.org/10.1039/D1DT03195C.[2] Arbresha Muriqi and Michael Nolan, “Role of Titanium and Organic Precursors in Molecular Layer Deposition of “Titanicone” Hybrid Materials”, Beilstein Journal of Nanotechnology, 2022, 13, 1240–1255. doi.org/10.3762/bjnano.13.103.

Influence of Surface Roughness, Nanostructure, and Wetting on Bacterial Adhesion.

Bacterial fouling is a persistent problem causing the deterioration and failure of functional surfaces for industrial equipment/components; numerous human, animal, and plant infections/diseases; and energy waste due to the inefficiencies at internal and external geometries of transport systems. This work gains new insights into the effect of surface roughness on bacterial fouling by systematically studying bacterial adhesion on model hydrophobic (methyl-terminated) surfaces with roughness scales spanning from ∼2 nm to ∼390 nm. Additionally, a surface energy integration framework is developed to elucidate the role of surface roughness on the energetics of bacteria and substrate interactions. For a given bacteria type and surface chemistry; the extent of bacterial fouling was found to demonstrate up to a 75-fold variation with surface roughness. For the cases showing hydrophobic wetting behavior, both increased effective surface area with increasing roughness and decreased activation energy with increased surface roughness was concluded to enhance the extent of bacterial adhesion. For the cases of superhydrophobic surfaces, the combination of factors including (i) the surpassing of Laplace pressure force of interstitial air over bacterial adhesive force, (ii) the reduced effective substrate area for bacteria wall due to air gaps to have direct/solid contact, and (iii) the reduction of attractive van der Waals force that holds adhering bacteria on the substrate were summarized to weaken the bacterial adhesion. Overall, this study is significant in the context of designing antifouling coatings and systems as well as explaining variations in bacterial contamination and biofilm formation processes on functional surfaces.

First Principles Modelling of Growth of Alucone Thin Films from Aromaticalcohol and Amine Precursors

Hybrid materials composed of organic and inorganic components offer the opportunity to develop interesting materials with well-controlled properties. Molecular Layer Deposition (MLD) is a suitable technique for the controlled growth of thin, conformal hybrid films. Despite growing interest in these materials, there is, however, insufficient understanding of the atomistic mechanism of MLD film growth.In this contribution, we present a first principles investigation of the molecular mechanism of the growth of hybrid organic−inorganic thin films of aluminium alkoxides, known as ”alucones”, grown by MLD. We investigate in detail the chemistry of the MLD process between the post-TMA pulse methyl-terminated Al2O3 surface and the homo- or hetero- bifunctional aromatic compounds with hydroxy and/or amino groups as reactive groups: hydroquinone (HQ), 4-aminophenol (AP) and p-phenylenediamine (PDA). Double reactions of HQ, AP and PDA with the alumina surface are explored in detail to assist the interpretation of the experimental findings regarding the differences in alucone films grown with HQ, AP and PDA. DFT calculations show that all aromatic precursor molecules bind favorably to the methyl terminated Al2O3, via formation of Al-O and Al-N bonds and CH4 elimination. However, reaction energetics suggest lower reactivity of the amino groups with TMA in comparison to the hydroxyl groups. Therefore, we expect that in the case of the heterobifunctional precursor, AP, for which one of the groups is more reactive (OH) than the other (NH2), the unwanted double surface reactions are reduced and the organic molecule can be self-assembled in a more up-right configuration, which leads to higher growth per rates. We also analyze the reactions between the methyl-terminated Al2O3 with 2-methylhydroquinone, 2-methoxyhydroquinone, 2-chlorhydroquinone and 2-nitrohyrdoquinone to examine the influence of the activating groups –CH3, -OCH3 and deactivating groups –Cl and –NO2 on the interaction between the O site of the organic molecule and the Al site of TMA. This study contributes to the understanding of growth process of HQ-alucones, AP-alucones and PDA-alucones at the molecular level and is valuable in supporting experimental data on hybrid film growth.

Single Nucleotides Moving through Nanoslits Composed of Self-Assembled Monolayers via Equilibrium and Nonequilibrium Molecular Dynamics.

Nonequilibrium molecular dynamics (MD) simulations were used to study the effect of three chemical surface groups on the separation of DNA mononucleotide velocity (or time-of-flight) distributions as they pass through nanoslits. We used nanoslits functionalize with self-assembled monolayers (SAMs) since they have relatively smooth surfaces. The SAM molecules were terminated with either a methyl, methylformyl, or phenoxy group, and the nucleotides were driven electrophoretically with an electric field intensity of 0.1 V/nm in slits about 3 nm wide. Although these large driving forces are physically difficult to achieve experimentally, the simulations are still of great value as they provide molecular level insight into nucleotide translocation events and allow comparison of different surfaces. Nucleotides adsorbed and desorbed from the slit surface multiple times during the simulations. The required slit length for 99% accuracy in identifying the deoxynucleotide monophosphates (dNMPs), based on the separation of the distributions of time of flight, was used to compare the surfaces with shorter lengths indicating more efficient separation. The lengths were 6.5 μm for phenoxy-terminated SAMs, 270 μm for methylformyl-terminated SAMs, and 2400 μm for methyl-terminated SAMs. Our study showed that a slit with a section with methyl termination and the second section with methylformyl termination lead to a required length of 120 μm, which was significantly lower than for only a methylformyl- or methyl-terminated surface.

Self-limiting growth when using trimethyl bismuth (TMBi) in the metal-organic vapor phase epitaxy (MOVPE) of GaAs1−yBiy

Theoretical and experimental studies have confirmed that the GaAs1−yBiy semiconductor alloy system has potential for long wavelength applications and devices with improved performance over other materials emitting at similar wavelengths. The growth of GaAs1−yBiy by metal-organic vapor phase epitaxy (MOVPE) remains a challenge; bismuth is not easily incorporated into the GaAs matrix due the large difference in electronegativity and covalent radii between As and Bi. These differences often lead to Bi surface segregation or very low incorporation rates of Bi into the GaAs matrix. We have studied the growth of GaAs1−yBiy quantum well structures using trimethyl bismuth as the Bi source. A reduced growth rate is observed with increasing Bi precursor flux into the growth reactor. Additionally, an increase in the growth time for the Bi-containing layer at very low growth temperatures does not lead to a corresponding increase in layer thickness, which is indicative of a near self-limiting growth. Complex compositional profiles deduced from combining x-ray diffraction analysis with the transmission electron microscopy investigations are used to develop a phenomenological model of the MOVPE growth of GaAs1−yBiy heterostructures which includes a complex interplay of the chemical surface species. The presence of a methyl-terminated surface, associated with the use of trimethyl Bi, particularly at low growth temperatures, leads to an effective “site blocking” by Bi precursor inhibiting the growth of GaAs1−yBiy hetero-structures.

Differential Adsorption of Small Molecules in Spatially Functionalized Porous Silicon Nanostructures

An experimental approach to rapidly quantify the relative affinity of a small molecule analyte for two different surfaces is described. The method uses optical measurements of high surface area porous Si thin films that contain two spatially distinct surface chemistries. The chemistries are placed on the walls of the ∼10 nm diameter pores of the porous Si film by means of microdroplet patterning, where a chemical resist is drop-coated on the porous Si sample to define distinct regions across the plane of the chip. In this work, the two chemistries consist of a hydrophilic silicon oxide surface and a hydrophobic methyl-terminated silicon surface. Detection is achieved by simultaneous optical reflectance measurements of both regions, where the reflectance spectrum contains a convolution of the Fabry-Pérot interference spectrum of both the oxide and the methyl-grafted layers. The differential partitioning of a test analyte (2-acetoxybenzoic acid or diphenyl ether) from aqueous solution is determined from the Fourier transform of the optical interference spectrum. The approach is rapid and nondestructive, and it can be performed on a small sample volume as a means to quantify the partition behavior of small molecules.

Surface Initiation from Adsorbed Polymer Clusters: A Rapid Route to Superhydrophobic Coatings

We introduce the use of a hydroborated polyisoprene (PIP) macroinitiator for the rapid surface-initiated growth of superhydrophobic polymethylene (PM) films. Rinsing of a dip-coated PIP film on a methyl-terminated surface atop silicon or gold substrates results in robustly bound, isolated PIP clusters. After hydroboration of the internal olefins, these clusters result in extremely rapid growth of polymethylene coatings upon exposure to a diazomethane solution in diethyl ether at -17 °C. The resulting PM films achieve 6 μm thicknesses within 20 min of polymerization and become superhydrophobic with advancing and receding water contact angles of 166° and 156°, respectively, within 1 min. The PM films grown from these PIP clusters exhibit 3× greater propagation velocities, 30% lower termination rates, and more highly textured morphologies than PM films grown from hydroborated monolayers.

Examining the frictional forces between mixed hydrophobic – hydrophilic alkylsilane monolayers

Monolayers presenting methyl-terminated (hydrophobic) and hydroxyl-terminated (hydrophilic) surfaces on silica have been studied by molecular dynamics simulation and the effects of hydrogen bonding, chain length, and chain mixing on the frictional properties determined. The hydroxyl-terminated monolayers were found to show large adhesion zones as a result of strong interfacial interlayer hydrogen bonds; the interfacial sliding forces observed in the hydroxyl-terminated monolayers being one order of magnitude higher than the interfacial forces for the hydrophobic surfaces at the characteristic point of zero-load. Mixed hydroxyl- and methyl-terminated monolayers of equal length were found to exhibit intermediate shear stress values between those observed for pure monolayers, with the magnitude of the shear stress depending on the surface content of the hydroxyl-terminated chains. For mixed monolayers of unequal chain lengths, at high loads a maximum in the magnitude of the shear stress as a function of the length of the methyl-terminated chain was observed due to the creation of a buffer zone between the hydroxyl-terminated chains that produces strong hydrogen-bonding interactions. The effect of a constant normal load or constant separation simulation ensemble on the results has also been studied and in general found to have minimal influence on the observed behavior, although some differences are observed for the shear stress at intermediate normal loads due to the formation of stronger hydrogen bond networks at constant load compared to constant separation.

Photochemical Grafting and Patterning of Organic Monolayers on Indium Tin Oxide Substrates

Covalently attached organic layers on indium tin oxide (ITO) surfaces were prepared by the photochemical grafting with 1-alkenes. The surface modification was monitored with static water contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurements. Hydrophobic methyl-terminated ITO surfaces can be obtained via the grafting of tetradec-1-ene, whereas the attachment of ω-functionalized 1-alkenes leads to functionalized ITO surfaces. The use of a C≡C-Ge(CH(3))(3) terminus allows for facile tagging of the surface with an azido group via a one-pot deprotection/click reaction, resulting in bio/electronically active interfaces. The combination of nonaggressive chemicals (alkenes), mild reaction conditions (room temperature), and a light-induced grafting that facilitates the direct patterning of organic layers makes this simple approach highly promising for the development of ITO-based (bio)electronic devices.

Large surface photovoltages observed at methyl-terminated silicon surfaces synthesised through a two-step chlorination-alkylation method

Methylation of the silicon surface through a chlorination-alkylation method has been used to improve the electronic properties of silicon. Upon alkylation of the surface, an increase in the minority carrier recombination lifetime and the surface photovoltage is observed, in line with an increase in surface charge. A likely explanation of this unusually large band bending is charge accumulation during the removal of chlorine from the surface.

Adsorption Behavior of Hydrophobically Modified Polyelectrolytes onto Amino- or Methyl-Terminated Surfaces

The adsorption of hydrophobically modified polyelectrolytes derived from poly(maleic anhydride-alt-styrene) (P(MA-alt-St)) containing in their side chain aryl-alkyl groups onto amino- or methyl-terminated silicon wafers was investigated. The effect of the spacer group, the chemical nature of the side chain, molecular weight of polyelectrolyte, and ionic strength of solution on the polyelectrolyte adsorbed amount was studied by null ellipsometry. The adsorbed amount of polyelectrolyte increased with increasing ionic strength, in agreement with the screening-enhanced adsorption regime, indicating that hydrophobic interactions with the surface play an important role in the adsorption process. At constant ionic strength, the adsorbed amount was slightly higher for polyelectrolytes with larger alkyl side chain and decreased with the hydrophobicity of aryl group. The adsorption behavior is discussed in terms of the side chain flexibility of the polymer. Characteristics of the adsorbed layer were studied by atomic force microscopy (AFM) and contact angle measurements. AFM images show the presence of aggregates and closed globular structure of polyelectrolyte onto the amino- or methyl-terminated surface, which agrees with a 3D and 2D growth mechanism, respectively. Fluorescence measurements showed that the aggregation of polyelectrolyte containing the hydrophobic naphthyl group occurs already in the solution. However, the aggregation of polyelectrolytes containing the phenyl group in its side chain is not observed in solution but is induced by the amino-terminated surface. This difference can be explained in terms of the higher flexibility of side chain bearing the phenyl group. The polyelectrolyte films showed a high chemical heterogeneity and moderate hydrophobicity.

Osteopontin presentation affects cell adhesion—Influence of underlying surface chemistry and nanopatterning of osteopontin

Osteopontin is a promising coating material for biomaterials, being important both in remodeling and formation of mineralized tissue and in immunological responses. We have investigated cell attachment to osteopontin adsorbed at different surface chemistries (-NH(2), -COOH, -CH(3), and bare gold) and to osteopontin presented as a nanopattern of 50 nm protein patches separated by a nonadhesive background. MDA-MB-435 cells adhere well to osteopontin presented at the hydrophilic chemistries (-NH2, -COOH, and gold) suggesting that osteopontin is presented in a functional form on these surfaces. On the amine surface, the cell attachment appears partly driven by electrostatic attraction between the positively charged substrate and the negatively charged cell membrane, whereas the spreading of the cells depends on the specific interaction with osteopontin presented at the surface. Significantly, fewer cells adhere to osteopontin presented at the methyl-terminated hydrophobic surface and the cells are less spread. On the nanopatterned osteopontin, only a very low number of cells adhered and those few attached cells showed an elongated morphology with few adhesion points to the surface. This indicates that the adhesive patches are not large enough to support stable focal contacts. The good cell attachment and spreading on the hydrophilic surfaces holds promise for osteopontin as a future coating for biomaterials.

Area-Selective Atomic Layer Deposition of Lead Sulfide: Nanoscale Patterning and DFT Simulations

Area-selective atomic layer deposition (ALD) of lead sulfide (PbS) was achieved on octadecyltrichlorosilane (ODTS)-patterned silicon substrates. We investigated the capability of ODTS self-assembled monolayers (SAMs) to deactivate the ALD PbS surface reactions as a function of dipping time in ODTS solution. The reaction mechanism was investigated using density functional theory (DFT), which showed that the initial ALD half-reaction is energetically unfavorable on a methyl-terminated SAM surface. Conventional photolithography was used to create oxide patterns on which ODTS SAMs were selectively grown. Consequently, PbS thin films were grown selectively only where ODTS was not present, whereas deposition was blocked in regions where ODTS was grown. The resulting fabricated patterns were characterized by scanning electron microscopy and Auger electron spectroscopy, which demonstrated that ALD PbS was well confined to defined patterns with high selectivity by ODTS SAMs. In addition, AFM lithography was employed to create nanoscale PbS patterns. Our results show that this method can be applied to various device-fabrication processes, presenting new opportunities for various nanofabrication schemes and manifesting the benefits of self-assembly.

Energetics and stability of pentacene thin films on amorphous and crystalline octadecylsilane modified surfaces

Charge transport in organic thin film transistors (OTFTs) is directly related to the morphology and growth of the organic semiconductor at the dielectric interface. The most commonly used dielectric interface in OTFT research is alkylsilane-modified silicon oxide (SiO2). In this report, the nucleation, energetics, and stability of pentacene thin films on methyl-terminated surfaces are discussed. The density of the terminal methyl group was found to be an important parameter for controlling the growth of organic semiconductors. Pentacene growth is two-dimensional (2D) on SiO2 dielectrics modified with a crystalline, densely packed octadecylsilane (OTS) monolayer. However, it is primarily three-dimensional (3D) on SiO2 dielectrics modified with an amorphous OTS layer. Beyond a critical OTS density, the interaction between the OTS and pentacene exceeds the pentacene interlayer interaction energy engendering 2D growth which is preferential for high charge carrier mobility. The nucleation density is also much higher on the crystalline OTS compared to the amorphous OTS. The sub-monolayer thin films of pentacene were found to be much more stable on the ordered OTS compared to disordered OTS. Atomic force microscopy (AFM) and Monte Carlo simulations were used to develop a thorough analysis of pentacene film growth and energetics on OTS surfaces.

Organosilane self-assembled multilayer formation based on activation of methyl-terminated surface with reactive oxygen species generated by vacuum ultra-violet excitation of atmospheric oxygen molecules

A xenon excimer lamp which irradiates vacuum ultra-violet (VUV) light at 172 nm in wavelength was applied to the photochemical surface conversion of n-octadecyltrimethoxysilane self-assembled monolayer (ODS-SAM) in the presence of atmospheric oxygen and subsequent multilayer fabrication. The terminal functional groups of ODS-SAM, –CH 3 groups, were converted into polar functional groups, like –COOH, by the reaction with atomic oxygen species generated photochemically through VUV excitation of atmospheric oxygen molecules. The structure of the resulting organosilane multilayer with different numbers of superimposed monolayers (from 1 to 11), prepared on a smooth and hydrophilic silicon substrate by the layer-by-layer (LbL) approach, was examined in terms of molecular organization as well as the intra- or interlayer binding modes in such novel films. Ellipsometry and grazing angle X-ray reflectivity measurements revealed that multilayer films of up to 11 discrete monolayers were successfully obtained, indicating that the self-assembly is a viable technique for the construction of relatively thick (16 nm and above) multilayer films.

Adhesion of human leukocytes on mixtures of hydroxyl‐ and methyl‐terminated self‐assembled monolayers: Effect of blood protein adsorption

The adhesion of human leukocytes to nanostructured surfaces with different chemical properties and the effect of protein adsorption were investigated. Self-assembled monolayers (SAMs) prepared with mixtures of methyl- and hydroxyl-terminated alkanethiols in different percentages on gold were used. The surfaces were pre-immersed in distinct protein solutions (human serum albumin, human fibrinogen, and autologous plasma). Adherent leukocytes were analyzed both by light and SEM. SAMs submitted to pre-immersion in plasma presented higher numbers of adherent leukocytes in the pure OH-terminated SAM, whereas methyl-terminated surfaces accounted for the lowest number of adherent cells. We observed a general increase in the number of adherent human leukocytes as the percentage of OH groups on the surface of the SAMs increased for all the pre-immersion conditions investigated. The number of adherent human leukocytes is highly influenced by the pre-immersion conditions used, and this observation is particularly relevant in the case of the methyl-terminated SAMs. The results obtained demonstrate that surface chemistry has a major influence in leukocyte adhesion to biomaterials, and that pre-immersion in protein solutions has a determinant effect in leukocyte adhesion.

Friction force microscopy of lubricin and hyaluronic acid between hydrophobic and hydrophilic surfaces

Lubricin and hyaluronic acid (HA), molecular constituents of synovial fluid, have long been theorized to play a role in joint lubrication and wear protection. While lubricin has been shown to function as a boundary lubricant, conflicting evidence exists as to the boundary lubricating ability of hyaluronic acid. Here, we use colloidal force microscopy to explore the friction behavior of these two molecules on the microscale between chemically uniform hydrophilic (hydroxyl-terminated) and hydrophobic (methyl-terminated) surfaces in physiological buffer solution. Behaviors on both surfaces are physiologically relevant since the heterogeneous articular cartilage surface contains both hydrophilic and hydrophobic elements. Friction between hydrophobic surfaces was initially high (μ=1.1, at 100nN of applied normal load) and was significantly reduced by lubricin addition while friction between hydrophilic surfaces was initially low (μ=0.1) and was slightly increased by lubricin addition. At lubricin concentrations above 200 µg/ml, friction behavior on the two surfaces was similar (μ=0.2) indicating that nearly all interaction between the two surfaces was between adsorbed lubricin molecules rather than between the surfaces themselves. In contrast, addition of HA did not appreciably alter the frictional behavior between the model surfaces. No synergistic effect on friction behavior was seen in a physiological mixture of lubricin and HA. Lubricin can equally mediate the frictional response between both hydrophilic and hydrophobic surfaces, likely fully preventing direct surface-to-surface contact at sufficient concentrations, whereas HA provides considerably less boundary lubrication.

Self-Assembled Monolayers Directly Attached to Silicon Substrates Formed from 1-Hexadecene by Thermal, Ultraviolet, and Visible Light Activation Methods

Using 1-hexadecene as a precursor, self-assembled monolayers (SAMs) were fabricated on hydrogen-terminated silicon (111) [H-Si(111)] surfaces without forming an interfacial oxide layer on the basis of thermal (180 °C, 2 h), ultraviolet (UV; 500 mW cm-2, 10 h), and visible-light activation (330 mW cm-2, 16 h) processes. As characterized by water contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and ellipsometry, the hexadecyl SAM fabricated by the visible-light process had a highly-ordered molecular arrangement and a closely-packed methyl-terminated surface similar to the SAMs prepared by the thermal and UV activation processes. The photo-irradiation wavelength dependence of the visible-light activation process was further studied at irradiation wavelengths of 400, 550, and 700 nm. The SAM formation reaction was certainly promoted at all the wavelengths, even at 700 nm. However, oxidation of the Si surface became apparent due to the slow rate in SAM growth, and thus the monolayer coverage of SAM at 700 nm became smaller. The reaction rate became faster with the decreasing wavelength for activation, probably due to the increase in the light adsorption coefficient of Si. The excitation of Si, namely, the generation of hole/electron pairs at the Si substrate, is assumed to be the rate-controlling step of the visible-light activation process.

Covalent Attachment of Organic Monolayers to Silicon Carbide Surfaces

This work presents the first alkyl monolayers covalently bound on HF-treated silicon carbide surfaces (SiC) through thermal reaction with 1-alkenes. Treatment of SiC with diluted aqueous HF solutions removes the native oxide layer (SiO2) and provides a reactive hydroxyl-covered surface. Very hydrophobic methyl-terminated surfaces (water contact angle theta = 107 degrees ) are obtained on flat SiC, whereas attachment of omega-functionalized 1-alkenes also yields well-defined functionalized surfaces. Infrared reflection absorption spectroscopy, ellipsometry, and X-ray photoelectron spectroscopy measurements are used to characterize the monolayers and show their covalent attachment. The resulting surfaces are shown to be extremely stable under harsh acidic conditions (e.g., no change in theta after 4 h in 2 M HCl at 90 degrees C), while their stability in alkaline conditions (pH = 11, 60 degrees C) also supersedes that of analogous monolayers such as those on Au, Si, and SiO2. These results are very promising for applications involving functionalized silicon carbide.

Differential adsorption of variants of the Thermomyces lanuginosus lipase on a hydrophobic surface suggests a role for local flexibility

Lipases are activated at interfaces between aqueous and hydrophobic phases, where they typically undergo conformational changes leading to significant activity increase. Here I use a quartz crystal microbalance with dissipation (QCM-D) to study changes in layer thickness and viscosity during the adsorption of variants of the Thermomyces lanuginosus lipase (TlL) onto a methyl-terminated hydrophobic surface. Unlike wildtype TlL, the variant Mut1, which shows improved performance under certain test conditions, shows a large dissipation increase during the binding process, leading to a significantly thicker layer. This altered adsorption behaviour may be linked to Mut1's changes in secondary structure. This is corroborated by the fact that four other TlL mutants with unaltered secondary structure showed wildtype-like absorption behaviour. Unlike wildtype TlL and the other variants, Mut1 contains several consecutive basic residues introduced into the C-terminal region which is close in space to the N-terminal part of the protein, which also contains several basic residues. Electrostatic repulsion between these two regions leading to local structural flexibility may facilitate altered adsorption behaviour and ultimately to improved enzymatic performance on a solid surface. QCM-D thus provides a good approach to screen protein variants for their adsorption properties on hydrophobic surfaces.