Nanoscale biofilm modification-method concerning a myoglobin/11-MUA bilayers for bioelectronic device

We developed surface modification tools for the fabrication of a bioelectronic device which consists of a myoglobin monolayer self-assembled on an 11-MUA layer. To utilize a single protein as the active element, it was necessary to reduce protein aggregation on the protein layer in the nanobio electronic device, which was developed in our previous study and shown to display basic biomemory functions. Here, the reduction of myoglobin aggregation was accomplished by using 3-(3-cholamidopropyl) dimethylammonio-11-propanesulfonate (CHAPS) to fabricate a well-defined protein layer on the bioelectronic device. We investigated two different surface modification methods for making well oriented biofilm. The effects of CHAPS on the formation of a myoglobin layer self-assembled on an 11-MUA layer were examined by atomic force microscopy and Raman spectroscopy. The size of the myoglobin aggregates was reduced from 200-250 nm to 10-40 nm depending on treatment method. The sustaining redox property of the CHAPS treated myoglobin layer was examined using cyclic voltammetry. Using these techniques, we found that after surfactant CHAPS treatment, protein aggregation was dramatically reduced and the protein layer still maintained its inherent electrochemical properties.     

Preparation of a self-assembled cytochrome c monolayer on a gold substrate for biomolecular device architecture

The segregation ability of 3-[(3-cholamidopropyl) dimethylammonio]-1-propanesulfonate (CHAPS), a zwitterionic surfactant, on cytochrome c (cyt c) aggregates in a phosphate buffer solution was quantified through the dynamic light-scattering analysis, and CHAPS was found to have an excellent ability in reducing nonspecific affinity among cyt c molecules. When CHAPS was applied to cyt c aggregates on the surface of gold substrates modified with self-assembled cyt c monolayer, the aggregates were found to be successfully eliminated by high-resolution atomic force microscopy image with 30-nm-sized cyt c clusters. This technique is expected to be useful to prepare a self-assembled monolayer of metalloproteins without their aggregates which may degrade the electrochemical property required as a biomolecular electronic device.     

Conformational morphology of polyaniline grown on self-assembled monolayer modified silicon

Polyaniline (PANI) films with pyramidal shaped crystallites were prepared by self-organization on self-assembled monolayer (SAM) modified Si substrates. High-resolution atomic force microscopy (HR-AFM) shows that SAM has tridymite structural order and the PANI film has biphasic conformational morphology corresponding to face-on orientation and edge-on orientation. Order parameters obtained from power spectral density analysis of HR-AFM images of SAM and PANI films show that the pyramidal crystallites are in emeraldine salt (ES-I) form and the region between the crystallites is in emeraldine base (EB-II) form. The ordered lattice of PANI crystallites as observed by cross-sectional HR-TEM confirms its single crystalline nature as well as epitaxial growth. The heteroepitaxial growth of PANI is attributed to the structural order of interfacial SAM on Si.     

An immunosensor for haemoglobin based on impedimetric properties of a new mixed self-assembled monolayer

A novel impedimetric immunosensor for the detection of haemoglobin has been developed by mixed self-assembled monolayers on Au. First, a mixed self-assembled monolayer (SAMs) consisting of 1,2 dipalmitoyl-sn-glycero-3-phosphoethanolamine-N-(biotinyl) (biotinyl-PE) and 16-mercaptohexadecanoic acid (MHDA) on gold electrodes was studied. The conformational properties of the SAMs were characterised by cyclic voltammetry and impedance spectroscopy. After blocking non-specific binding sites in the mixed monolayer using non-specific IgG, neutravidin was used to bind to biotinyl sites present in the mixed monolayer. Finally, biotinylated anti-haemoglobin IgG was immobilised to the tethered neutravidin. The membrane resistance R_m, obtained from the assembly, decreased gradually after the addition of non-specific IgG, neutravidin and anti-haemoglobin to the monolayer. This decrease could be attributed to a rearrangement in the structure of the SAMs. The detection of antibody–antigen reaction demonstrates that the potentiometric immunosensor exhibited high sensitivity and a detection limit of 20 ng/ml (approximately 0.3 nM).     

Patterning of ITO films on flexible substrates by using self-assembled monolayer

The patterning of indium tin oxide (ITO) films on flexible polyester (PET) substrates by using a self-assembled monolayer (SAM) of octadecyltrimethoxysilane (OTMS) was investigated. After a SAM is deposited on ITO films, the ITO surface hydrophilicity and electron transfer characteristics are altered. The contact angle and electrochemical cyclic voltammetry analyses indicate the optimal process to form a SAM on ITO films operated in a low-humidity environment at 25 ºC for 24 h. The AFM observation shows that the ITO films covered by a SAM can be protected during etching in an oxalic solution, which means a SAM can well play the role of a photoresist during lithographic process.     

Surface-enhanced Raman scattering substrate based on a self-assembled monolayer for use in gene diagnostics

The development of surface-enhanced Raman scattering (SERS)-active substrates for cancer gene detection is described. The detection method uses Raman active dye-labeled DNA gene probes, self-assembled monolayers, and nanostructured metallic substrates as SERS-active platforms. The mercaptohexane-labeled single-stranded DNA (SH-(CH(2))(6)-ssDNA)/6-mercapto-1-hexanol system formed on a silver surface is characterized by atomic force microscopy. The surface-enhanced Raman gene (SERGen) probes developed in this study can be used to detect DNA targets via hybridization to complementary DNA probes. The probes do not require the use of radioactive labels and have a great potential to provide both sensitivity and selectivity. The effectiveness of this approach and its application in cancer gene diagnostics (BRCA1 breast cancer gene) are investigated.     

Optical properties of an octadecylphosphonic acid self-assembled monolayer on a silicon wafer

We report a study of a full-coverage octadecylphosphonic acid (OPA or ODPA) self-assembled monolayer (SAM) spin-coated on the native oxide layer (SiO₂) of a single crystalline silicon (c-Si) wafer using spectroscopic ellipsometry (SE) and reflectometry (SR). The OPA SAM showed characteristics of being a dielectric film in visible range and becoming absorbing in deep-UV range. By assuming an optical stack model of OPA/SiO₂/c-Si for the OPA monolayer system and adopting the parameterized Tauc-Lorentz dispersion model, we obtained an excellent fit of the model to the SE and SR data, from which dispersion of optical functions as well as thickness of the OPA film were deduced. The OPA film thickness measured by atomic force microscopy (AFM) on partial coverage OPA samples was used as the initial trial film thickness in the fitting processes. The deduced OPA film thickness from SE and SR data fitting was in good agreement with that obtained by AFM.     

自组装囊泡的结构与单分子膜的性质

研究了具有不同主链分子量和侧链长度的N,N-双烷基化壳聚糖单分子膜的性质.结果表明,主链分子量越大,所形成的N,N-双烷基壳聚糖单分子膜的结构越紧密.在主链分子量相同的条件下,N,N-双烷基壳聚糖单分子膜的致密度随着侧链长度的增大而增大,表明N,N-双烷基化壳聚糖分子间的缠结嵌套和疏水相互作用力的增大.比较N,N-双烷基化壳聚糖单分子膜与相应自组装囊泡的性质发现,囊泡的药物平衡释放率随着其相应材料单分子膜压缩模量的增大而减小,呈现出一定的线性关系.单分子膜压缩模量的大小反映囊泡膜结构的紧密程度.     

A high-coverage nanoparticle monolayer for the fabrication of a subwavelength structure on InP substrates

Subwavelength structures (SWSs) were fabricated on the Indium Phosphide (InP) substrate by utilizing the confined convective self-assembly (CCSA) method followed by reactive ion etching (RIE). The surface condition of the InP substrate was changed by depositing a 30-nm-thick SiO2 layer and subsequently treating the surface with O2 plasma to achieve better surface coverage. The surface coverage of nanoparticle monolayer reached 90% by using O2 plasma-treated SiO2/InP substrate among three kinds of starting substrates such as the bare InP, SiO2/InP and O2 plasma-treated SiO2/InP substrate. A nanoparticle monolayer consisting of polystyrene spheres with diameter of 300 nm was used as an etch mask for transferring a two-dimensional periodic pattern onto the InP substrate. The fabricated conical SWS with an aspect ratio of 1.25 on the O2 plasma-treated SiO2/InP substrate exhibited the lowest reflectance. The average reflectance of the conical SWS was 5.84% in a spectral range between 200 and 900 nm under the normal incident angle.     

Electrochemical studies of cystine modified self-assembled monolayer for Escherichia coli detection

An electrochemical DNA biosensor based on cystine modified self-assembled monolayer (cys-SAM) onto gold electrode (AuE) has been fabricated for Escherichia coli (E. coli) detection. This biosensing electrode has been characterized using scanning electron microscopy (SEM), FT-IR spectroscopy, cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). Under the optimum conditions, this DNA biosensor can be used to detect complementary target DNA concentration in the range of 1 × 10^− 6 M to 1 × 10^− 20 M within 60 s of hybridization time at 25 °C and has been found to be stable for about four months when stored at 4 °C.     

High-resolution TOF-SIMS study of varying chain length self-assembled monolayer surfaces

A high-resolution time-of-flight secondary ionization mass spectrometer (TOF-SIMS) has been used to investigate chain length effects in hydrocarbon seff-assembled monolayer (SAM) surfaces on gold substrates. A wide range of n-alkanethiols was used to make homogeneous SAM surfaces, which included both odd and even hydrocarbon chain length thiols. Variations in coverage, extent of oxidation, and high-mass cluster formation as a function of hydrocarbon chain length of the alkanethiol SAM surfaces were investigated. Long-short chain length effects were observed for the relative coverage of the SAM surfaces, which directly influences the extent of oxidation for the thin films. The formation of gold-sulfur and gold-adsorbate cluster ions was also observed, since the mass range of the TOF-SIMS made it possible to monitor all of the cluster ions that were formed following the high-energy ion/surface interactions.     

Unexpected effect of copper ions on electrochemical impedance behaviour of self-assembled alkylaminethiol monolayer

Effect of copper ions on the electrochemical behaviour of an alkylaminethiol monolayer has been studied by electrochemical impedance spectrosocpy. RAMAN experiment shows the effective adsorption of receptor onto the gold surfaces. The study of Nyquist plot shows that the gold/monolayer/electrolyte interface can be described by a serial combination of two R, CPE electrical circuits. In the presence of increasing amounts of copper, the Nyquist plots at low frequencies were modified showing an increase of the resistance of the second R, CPE electrical circuit. Moreover, this increase of resistance varies linearly with the amounts of copper ions added in solution from 10^? 8 mol·L^? 1 to 10^? 5 mol·L^? 1.     

Piezoelectric immunosensor based on gold nanoparticles capped with mixed self-assembled monolayer for detection of carcinoembryonic antigen

It is very important for a piezoelectric immunosensor to increase specific binding and decrease nonspecific adsorption. This study presents the development of such a piezoelectric immunosensor for the detection of carcinoembryonic antigen. An AT-cut quartz crystal's Au electrode surface was first modified with homogenous self-assembled monolayer of cysteamine (CE). Gold nanoparticles capped with mixed self-assembled monolayer of CE and MH (6-mercapto-1-haxanol) were then attached to the CE monolayer via glutaraldehyde (GA). Antibodies were immobilized onto a mixed self-assembled monolayer of CE and MH with GA as a reactive intermediate too. The binding of target antigens onto the immobilized antibodies decreased the sensor's resonant frequency, and the frequency shift was correlated to the antigen concentration. The stepwise assembly of the immunosensor was characterized by means of cyclic voltammetry technique. This immunoassay was shown to be specific and sensitive, thus providing a viable alternative to carcinoembryonic antigen detection method.     

Plasma-assisted fabrication of monolayer phosphorene and its Raman characterization

There have been continuous efforts to seek novel functional two-dimensional semiconductors with high performance for future applications in nanoelectronics and optoelectronics. In this work, we introduce a successful experimental approach to fabricate monolayer phosphorene by mechanical cleavage and a subsequent Ar＊ plasma thinning process. The thickness of phosphorene is unambiguously determined by optical contrast spectra combined with atomic force microscopy （AFM）. Raman spectroscopy is used to characterize the pristine and plasma-treated samples. The Raman frequency of the A2g mode stiffens, and the intensity ratio of A2g to Alg modes shows a monotonic discrete increase with the decrease of phosphorene thickness down to a monolayer. All those phenomena can be used to identify the thickness of this novel two-dimensional semiconductor. This work on monolayer phosphorene fabrication and thickness determination will facilitate future research on phosphorene.     

Effect of local environment on molecular conduction: isolated molecule versus self-assembled monolayer

Developing a fundamental understanding of molecular conduction in different device environments is essential to the advance of molecular electronics. We show through a quantitative comparison of two types of junctions with the same molecule - one based on an isolated individual molecule and the other on a self-assembled monolayer - that intrinsic differences in the conduction per molecule as large as several orders of magnitude can exist simply as a function of the presence or absence of neighboring molecules. This behavior can be understood on the basis of thermal and electrostatic effects that depend critically on the local molecular environment. These results will help to unify data obtained from disparate device structures and to provide an improved basis for designing future molecular electronic devices.     

Tantalum-filament pulling device for fabrication of submicrometer fused-silica tips

A simple and low-cost pulling device for fused-silica capillaries was developed. By using a tantalum heating filament and the self-tension in a bent capillary, tips and constricted regions with outer diameters of approximately 1 microm and inner diameters of a few hundred nanometers could be reproducibly pulled from 50-microm-i.d., 375-microm-o.d. capillaries. The tips can be used in different applications such as microinjection, micromanipulation, and single-channel patch-clamp, injection ends for CE or as electrospray tips. Constricted capillaries with optimized dimensions to minimize cylindrical lensing effects and to match the size of a diffraction-limited laser focus can be used as optical detection windows in CE and micro-HPLC. Fused silica has several advantages over other glasses such as high melting temperature and superior optical and mechanical properties.     

pH and iodide ion effect on corrosion inhibition of histidine self-assembled monolayer on copper

Self-assembled monolayer (SAM) of histidine (His) was prepared on copper surface at various pH values. The effect of KI additives on corrosion protection efficiency of His SAM was also studied. The protection abilities of these films against copper corrosion in 0.5 M HCl aqueous solution were investigated using electrochemical impedance spectroscopy and polarization techniques. The results show that the film formed on the electrode is more stable at pH = 10 than that at other pH values. When the iodide ions were added into the His self-assembly solution (pH = 10), protection efficiency was further improved. The inhibition mechanism has been discussed by quantum chemical calculations.