Preparation and characterization of APTES films on modification titanium by SAMs

In this study, the titanium plates, which were modified by NaOH alkali solution, were associated with 3-Aminopropyltriethoxysilane (APTES) films using self-assembled monolayers (SAMs). The surfaces of titanium before and after modification were characterized by scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and attenuated total refraction-Fourier transform infrared spectroscopy (ATR-FTIR). After bonding the APTES films on the modification titanium, the new peaks located around 1095 cm⁻¹ attributes to siloxane groups indicating that silane agent had been grafted onto the surface of the modification titanium substrate by SAMs. Following the deposition of APTES films on titanium, significant change were seen in the amounts of oxygen, silicon and carbon present on the titanium surface, which were consistent with the anticipated reaction steps.     

In-situ protein adsorption study on biofunctionalized surfaces using spectroscopic ellipsometry

Techniques currently employed to evaluate biomolecular interactions on surfaces require the use of radiolabeled, enzymatic, or fluorescent-tags to record and report the binding event. Ellipsometry has proven to be a powerful tool in understanding the biomolecular interactions on solid substrates and, typically does not require the labeling of the ligand or the receptor. In this present study, the adsorption kinetics of Human Serum Albumin (HSA) on functionalized silicon surfaces were evaluated using in-situ ellipsometry. In-situ ellipsometry was used to estimate the thickness of the adsorbed layers and the adsorption and desorption kinetics of HSA on functionalized surfaces. In this study, dense, self assembled monolayers were fabricated using aminopropyltriethoxysilane (APTES) and mixed silanes using APTES and methyltriethoxysilane at a ratio of 1:10, to serve as a template for protein immobilization on silicon surfaces. The silane derivatized surfaces were further modified using three different ligands/receptors that have been reported to bind HSA, namely: a linear peptide, a polyclonal antibody against human serum albumin, and small synthetic ligand (2, 4, 6-Tris(dimethylaminomethyl)phenol. The amount of HSA adsorbed was observed to increase with time, and with the initial concentration of the HSA solution. The adsorption kinetics of HSA on functionalized surfaces was approximated by a simple model for protein adsorption. A good model fit was obtained for the experimental data, thus enabling the interpretation of the adsorption kinetics of HSA on functionalized silicon surfaces. The effect of different HSA binding ligands on the rate constants affecting protein adsorption and desorption were studied.     

Characterization of trypsin immobilized on the functionable alkylthiolate self-assembled monolayers: A preliminary application for trypsin digestion chip on protein identification using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Self-assembled monolayers (SAMs) on coinage metal provide versatile modeling systems for studies of interfacial electron transfer, biological interactions, molecular recognition and other interfacial phenomena. Recently the bonding of enzyme to SAMs of alkanethiols onto Au electrode surfaces was exploited to produce a bio-sensing system. In this work, the attachment of trypsin to a SAMs surface of 11-mercaptoundecanoic acid was achieved using water soluble N-ethyl-N -(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide as coupling agent. The thickness of SAMs was determined by optical ellipsometer; contact angles of the modified Au surfaces were measured in air using a goniometer. The Second Harmony Generation data displays the last few percents of the alkylthiol molecules adsorbed and produced the complete monolayer by inducing the transition from a high number of gauche defects to an all-trans conformation. Using X-ray Photoelectron Spectroscopy (XPS) and Fourier-Transformed Infrared Reflection-Absorption and Attenuated Total Reflection Spectroscopes (FTIR-RAS and ATR), we examined the chemical structures of samples with different treatments. By matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), we demonstrated the digestion of bovine serum albumin (BSA) on the trypsin-immobilized SAMs surface.Experimental results have revealed that the XPS C1s core levels at 286.3 and 286.5 eV (Amine bond), 288.1 eV (Amide bond) and 289.3 eV (Carboxylic acid) illustrate the immobilization of trypsin. These data were also in good agreement with FTIR-ATR spectra for the peaks valued at 1659.4 cm^{– 1} (Amide I) and 1546.6 cm^{– 1} (Amide II). Using MALDI-TOF MS observations, analytical results have demonstrated the BSA digestion of the immobilized trypsin on the functionalized SAMs surface. For such surfaces, BSA was digested on the trypsin-immobilized SAMs surface, which shows the enzyme digestion ability of the immobilized trypsin. The terminal groups of the SAMs structure can be further functionalized with biomolecules or antibodies to develop surface-base diagnostics, biosensors, or biomaterials.     

单壁碳纳米管在基底表面的离散生长

通过旋涂硝酸铁异丙醇溶液于P型硅表面以获得均匀分布的催化剂颗粒,以CH4为反应气体采用CVD方法即可在P型硅表面均匀生长单壁碳纳米管,并且部分碳纳米管呈直立状.研究了催化剂浓度、生长基底、反应温度对单壁碳纳米管表面生长情况的影响.研究表明,催化剂浓度升高或采用二氧化硅替代P型硅为生长基底时,都会导致单壁碳纳米管生长的密度加大,而碳纳米管长度变短且更易贴附基底表面生长;随反应温度的提高碳纳米管的生长效率降低,并使得碳纳米管更易贴附基底表面生长.采用此方法制备的生长有直立碳纳米管的硅片作为扫描基底,在原子力显微镜敲击模式下利用拾取法成功制备了碳纳米管原子力显微镜针尖.     

Characteristics of electrodeposited single-walled carbon nanotube films

Thin films of chemically-functionalized single walled carbon nanotubes (SWNTs) were fabricated by using a direct current (DC) electrodeposition method. SWNTs were shortened and then functionalized with acid chloride group to combine with amine group-terminated gold substrate. The electrodeposited SWNT films were characterized by using Raman spectroscopy, attenuated total reflectance infrared (ATR/IR) spectrometry and atomic force microscopy. We demonstrated that the SWNT film was well distributed on an electrode with robust adhesion.     

Si nanocolumns as novel nanostructured supports for enzyme immobilization

Silicon nanocolumns have been used as novel supports for the high-density immobilization of enzymes. Silicon nanocolumns with diameters of ca. 50-100 nm and a height of 1 micron were constructed using glancing angle deposition. The surfaces were successively treated with 3-aminopropyltriethoxysilane (APTES) and then with an amine reactive polymer, poly(ethylene-alt-maleic anhydride), to attach soybean peroxidase (SBP) to the support. Optimal coverage of APTES, polymer, and SBP was obtained for incorporation of enzyme onto the sidewalls of the nanocolumns. SBP immobilized on the silicon nanocolumns demonstrated an enhancement in biocatalytic activity of 160% over that of the enzyme immobilized on flat silicon wafers with the same projected area. The enzymatic activity decreased with progressive washes for both supports. This decrease in the activity of enzyme was found to be primarily due to the intrinsic deactivation of immobilized enzyme on the silicon surface. Designing nanocolumns with optimal dimensions, spacing, and surface chemistry may lead to the development of high-density arrays of proteins for applications in biotechnology.     

Microwave-assisted functionalization of single-wall carbon nanotubes through diazonium

Single-wall carbon nanotubes (SWNTs) have been functionalized by a diazonium method through both a classical thermal reaction and a microwave-assisted reaction. The functionalized SWNTs have been characterized by nIR-Vis-UV absorption spectroscopy, Raman spectroscopy, and thermal gravimetric analysis. The results show that SWNTs are covalently functionalized through both reactions and that the microwave-assisted reaction is more rapid. Moreover, optimal choice of the reaction time can prevent the microwave irradiation from the adverse effect of subsequently removing the functional groups on the SWNT surface.     

Microstructured bioreactive surfaces: covalent immobilization of proteins on Au(1 1 1)/silicon via aminoreactive alkanethiolate self-assembled monolayers

Micrometer-scale patterns of a defined surface chemistry and structure were produced on both ultraflat Au(1 1 1) and on gold-coated monocrystalline silicon surfaces by a method combining microcontact printing, wet chemical etching and the replacement of etch-resist self-assembled monolayers (SAMs) by functionalized or reactive SAMs. Key steps in this methodology were characterized by X-ray photoelectron spectroscopy (XPS), ellipsometry and contact angle measurements. The covalent immobilization of (functional) biological systems on these surfaces was tested using an N-hydroxysuccinimide ester -functionalized disulphide (DSU), which covalently binds primary amines without the need for further activation steps. Atomic force microscope images of native collagen V single molecules immobilized on these patterned surfaces revealed both high spatial resolution and strong attachment to the monolayer/gold surface. Microcontact printing of DSU is shown to be feasible on specially prepared, ultraflat Au(1 1 1) surfaces providing a valuable tool for scanning probe experiments with biomolecules. The retention of enzymatic activity upon immobilization of protein was demonstrated for the case of horseradish peroxidase. The described approach can thus be used to confine biological activity to predetermined sites on microstructured gold/silicon devices – an important capability in biomedical and biomolecular research. © 1999 Kluwer Academic Publishers     

Microcontact printing and selective surface dewetting for large area electronic applications

A universal microstructuring approach was developed, which facilitates the patterning of surfaces by a combination of microcontact printing (mCP) and selective surface dewetting/wetting. Self-assembled monolayers (SAMs) were patterned on glass or silicon substrates by μCP. The regions coated by the SAMs turn hydrophobic, whereas the uncoated regions stay hydrophilic. Such functionalized surfaces facilitate selective deposition of polymers or resists. Polymethyl methacrylate and prepolymer polyurethane were selectively deposited on the hydrophilic regions of the substrate. The hydrophobic regions of the substrate stay uncoated. Subsequently, the resist was used to lift-off metallic microstructures in order to realize micro coils and electrodes for radio frequency information tags. The printed electrodes were used to define drain and source contacts of organic thin film transistors. The device characteristic of the organic transistors will be presented.     

Analysis of the biomineralization process on SWNT-COOH and F-SWNT films

In vitro biomineralization process was investigated on functionalized single wall nanotube (SWNT) films. The films were prepared by solvent casting method by using carboxylated and fluorinated nanotubes. SWNT films were characterized by means of electron microscopy, contact angle measurements and optical absorption. The in vitro assays were performed on cultured human alveolar bone-derived cells (HABDC) to determine the capabilities of carboxylated single-walled nanotubes (SWNTs-COOH) and fluorinated single-walled nanotubes (F-SWNTs) to promote the deposit of mineral-like tissue. The results showed that the cellular response of HABDC in secreting a mineralized extracellular matrix and their consequent mineralization is dependent on the degree of functionalization of the SWNTs. Differences were found related to the kind of sidewall functionalization. Both structures promoted hydroxyapatite formation, however, calcium uptake on SWNTs-COOH increased and it was related to crystal density. From our results, it is possible to infer that CNT functionalization opens a path to future developments in new bone graft materials and techniques.     

Covalent binding of single-walled carbon nanotubes to polyamide membranes for antimicrobial surface properties

We propose an innovative approach to impart nanomaterial-specific properties to the surface of thin-film composite membranes. Specifically, biocidal properties were obtained by covalently binding single-walled carbon nanotubes (SWNTs) to the membrane surface. The SWNTs were first modified by purification and ozonolysis to increase their sidewall functionalities, maximize cytotoxic properties, and achieve dispersion in aqueous solution. A tailored reaction protocol was developed to exploit the inherent moieties of hand-cast polyamide membrane surfaces and create covalent amide bonds with the functionalized SWNTs. The reaction is entirely aqueous-based and entails activation of the carboxylate groups of both the membrane and the nanomaterials to maximize reaction with ethylenediamine. The presence of SWNTs was verified after sonication of the membranes, confirming the strength of the bond between the SWNTs and the membrane surface. Characterization of the SWNT-functionalized surfaces demonstrated the attainment of membranes with novel properties that continued to exhibit high performance in water separation processes. The presence of surface-bound antimicrobial SWNTs was confirmed by experiments using E. coli cells that demonstrated an enhanced bacterial cytotoxicity for the SWNT-coated membranes. The SWNT membranes were observed to achieve up to 60% inactivation of bacteria attached to the membrane within 1 h of contact time. Our results suggest the potential of covalently bonded SWNTs to delay the onset of membrane biofouling during operation.     

Covalent immobilization of DNA onto functionalized mica for atomic force microscopy

The immobilization of DNA on the self-assembled monolayer of 3-aminopropyltrimethoxysilane (APTES) on mica wafer functionalized with glutaraldehyde (GA) by chemical bonding was studied by atomic force microscopy (AFM). The DNA used for our investigation was amplified by polymerase chain reaction, and primers were labeled with a -NH2 group at their 5' terminus. The surfaces were analyzed by X-ray photoelectron spectroscopy (XPS) and AFM. Results from XPS and AFM showed that the mica with the APTES and activated with GA can be formed, and the flatness of the mica can be adapted for AFM images. We found that the modified surface was capable of binding DNA molecules so that it withstood a thorough rinsing with a solution of sodium dodecylsulfate. Covalent binding between the aldehyde-terminated membrane and -NH2 groups at both ends of double-stranded DNA resulted in immobilization and straightening of the DNA.     

Formation of Transition Metal Cluster Adducts on the Surface of Single-walled Carbon Nanotubes: HRTEM Studies

We report the formation of chromium clusters on the outer walls of single-walled carbon nanotubes (SWNTs). The clusters were obtained by reacting purified SWNTs with chromium hexacarbonyl in dibutyl ether at 100°C. The functionalized SWNTs were characterized by thermogravimetic analysis, XPS, and high-resolution TEM. The curvature of the SWNTs and the high mobility of the chromium moieties on graphitic surfaces allow the growth of the metal clusters and we propose a mechanism for their formation.     

Aggregation behavior of chemically attached poly(ethylene glycol) to single-walled carbon nanotubes (SWNTs) ropes

The aggregation behavior of poly(ethylene glycol) (PEG)-grafted single-walled carbon nanotubes (SWNTs) was investigated by Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), and high-resolution transmission electron microscopy (HR-TEM). The hybrid functional material was synthesized by producing carboxylic acid groups at nanotube ends and side-wall defect sites, which provide reaction sites for various guest species, followed by a reaction with hydroxyl-terminated PEG in various solvents. FTIR and TGA analyses confirm that the PEG chains were covalently attached to the functionalized SWNTs ropes. Transmission electron microscopy (TEM) images of the PEG-grafted SWNTs revealed two different morphologies, depending on solvent quality: PEG and SWNT segments self-organize into ring-like structure in which the aggregated PEG core is surrounded by SWNT bundles, when freshly prepared PEG-grafted SWNTs are cast from benzene/tetrahydrofuran solvent mixture. Instead, the hybrid polymers form a highly dispersed morphology in selective solvents for SWNTs. The novel aggregation mode originates from strong association of polymer chains with nanotubes, as in the aggregation behavior of micro-phase separated copolymers in dilute solution.     

Superhydrophobic surfaces produced by applying a self-assembled monolayer to silicon micro/nano-textured surfaces

A novel way of producing superhydrophobic surfaces by applying a self-assembled monolayer (SAM) to silicon micro/nano-textured surfaces is presented in this paper. The micro/nano-textured surfaces on silicon substrates were generated by the aluminum-induced crystallization (AIC) of amorphous silicon (a-Si) technique. Octadecyltrichlorosilane (OTS) SAMs were then applied to the textured surfaces by dip coating. The topography and wetting properties of the resulting surfaces were characterized using scanning electron microscopy (SEM) and a video-based contact angle measurement system. The results show that by introducing OTS SAMs on the silicon micro/nano-textured surfaces, superhydrophobic surfaces with water contact angles (WCAs) of 155° were obtained, as compared to the WCAs of OTS-modified smooth silicon surfaces of about 112°. Surface topography was found to directly influence the WCA as predicted by the Cassie-Baxter model.      

Magnetic nanoparticle-based separation of metallic and semiconducting carbon nanotubes

We report a simple and scalable method for the separation of semiconducting single-walled carbon nanotubes (SWNTs) from metallic SWNTs using magnetic nanoparticles (MNPs) functionalized with polycationic tri-aminated polysorbate 80 (TP80). MNPs-TP80 are selectively adsorbed on acid-treated semiconducting SWNTs, which makes the semiconducting SWNTs be highly concentrated to over 95% under a magnetic field. Almost all the field effect transistor network devices, which were fabricated using separated semiconducting SWNTs, exhibited a p-type semiconducting behavior with an on/off ratio of higher than 10(4).     

Mimicking cell membrane-like structures on alkylated silicon surfaces by peptide amphiphiles

We present a new strategy for flexible attachment of peptide amphiphiles on functionalized silicon surfaces. This method involves the production of an alkylated surface on which a lipidated peptide can then be attached through hydrophobic interaction. We applied this to two derivatives of amphiphilic peptide molecules with the same amino acid sequence (A-A-A-A-G-G-G-E-R-G-D) but different in alkyl chain lengths (palmitic acid, undecanoic acid). The basis of this work was to develop substrates which are more biocompatible and bioactive. The ultra-thin peptide amphiphile films were characterized using electrical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (ATR-FTIR) spectroscopy. The results demonstrated that the length of the alkyl chain in the peptide amphiphile affects the packing and coverage of the peptides on the silicon surface.     

Functionalization of single-walled carbon nanotubes by citric acid/oxygen plasma treatment

A safe and simple method of functionalizing single-walled carbon nanotubes (SWCNTs) has been developed, that significantly increases their dispersibility in water. SWCNTs in pure ethanol are treated with a supersonic homogenizer and dried. Then they are wetted with weak citric acid solution. Finally an RF (13.56 MHz) citric acid/oxygen plasma reaction is carried out under optimum conditions. As a result, hydrophilic functional groups attach onto the SWCNT surfaces, which enhance their dispersibility in water. The attachment of functional groups is identified by the FT-IR spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis. The dispersibility and dispersion stability are studied by the precipitation tests, UV-visible spectroscopy, and transmission electron microscopy. These functionalized SWCNTs are expected to be used in various applications.     

Organosilane functionalization of halloysite nanotubes for enhanced loading and controlled release

The surfaces of naturally occurring halloysite nanotubes were functionalized with γ-aminopropyltriethoxysilane (APTES), which was found to have a substantial effect on the loading and subsequent release of a model dye molecule. APTES was mostly anchored at the internal lumen surface of halloysite through covalent grafting, forming a functionalized surface covered by aminopropyl groups. The dye loading of the functionalized halloysite was 32% greater than that of the unmodified sample, and the release from the functionalized halloysite was dramatically prolonged as compared to that from the unmodified one. Dye release was prolonged at low pH and the release at pH 3.5 was approximately three times slower than that at pH 10.0. These results demonstrate that organosilane functionalization makes pH an external trigger for controlling the loading of guest on halloysite and the subsequent controlled release.     

Transforming the fabrication and biofunctionalization of gold nanoelectrode arrays into versatile electrochemical glucose biosensors

High-density arrays of conducting nanoelectrodes (i.e., nanoelectrode arrays [NEAs]) have been developed on the surface of a single electrode for numerous electrochemical sensing paradigms. However, a scalable fabrication technique and robust biofunctionalization protocol are oftentimes lacking and thus many NEA designs have limited efficacy and overall commercial viability in biosensing applications. In this report, we develop a lithography-free nanofabrication protocol to create large arrays of Au nanoelectrodes on a silicon wafer via a porous anodic alumina template. To demonstrate their effectiveness as electrochemical glucose biosensors, alkanethiol self-assembled monolayers (SAMs) are used to covalently attach the enzyme glucose oxidase to the Au NEA surface for subsequent glucose sensing. The sensitivity and linear sensing range of the biosensor is controlled by introducing higher concentrations of long-chain SAMs (11-mercaptoundecanoic acid: MUA) with short-chain SAMs (3-mercaptopropionic acid: MPA) into the enzyme immobilization scheme. This facile NEA fabrication protocol (that is well-suited for integration into electronic devices) and biosensor performance controllability (via the mixed-length enzyme-conjugated SAMs) transforms the Au NEAs into versatile glucose biosensors. Thus these Au NEAs could potentially be used in important real-word applications such as in health-care and bioenergy where biosensors with very distinct sensing capabilities are needed.