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.     

The effect of phosphate ions on the electrochemical behaviour of brass in sulphate solutions

In this study, we have investigated the effect of phosphate ions on the corrosion behaviour of brass in 0.1 M Na₂SO₄ solution in acidic (pH 2.1), neutral (pH 7.2) and alkaline (pH 12.3) solutions. For this purpose, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) techniques were used. The surface morphology of the metal surface after exposed to corrosive medium was investigated by scanning electron microscopy (SEM). The effect of temperature has also studied in the temperature range from 293 K to 353 K. Some thermodynamic parameters were calculated and discussed. It was found that, PO₄^3? ions could inhibit the corrosion of brass in Na₂SO₄ solution. However, the inhibition efficiency decreased with increasing temperature. The inhibition effect of PO₄^3? ions was explained by complex formation between phosphate ions and corrosion products which physically adsorbed on the metal surface.     

Study on chemical vapor deposited copper films on cyano and carboxylic self-assembled monolayer diffusion barriers

Thin copper films were produced by chemical vapor deposition using the precursor Cu^IIbis-hexafluoroacetylacetonate on the SiO₂/Si substrate modified with cyano and carboxylic self-assembled monolayers (SAMs) as diffusion barriers. The characterizations of the deposited copper films were measured by various thin film analysis techniques, i.e., scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The comparison between copper deposited on SiO₂ and on the SAM-modified SiO₂ substrates indicates that the copper films tend to be deposited onto the SAM-modified substrate, which is further proved by the calculation results of the interaction energies of copper and the SAMs with density functional theory method.     

Low-voltage p- and n-type organic self-assembled monolayer field effect transistors

We report on p- and n-type organic self-assembled monolayer field effect transistors. On the base of quaterthiophene and fullerene units, multifunctional molecules were synthesized, which have the ability to self-assemble and provide multifunctional monolayers. The self-assembly approach, based on phosphonic acids, is very robust and allows the fabrication of functional devices even on larger areas. The p- and n-type transistor devices with only one molecular active layer were demonstrated for transistor channel lengths up to 10 μm. The monolayer composition is proven by electrical experiments and by high-resolution transmission electron microscopy, electron energy loss spectroscopy, XPS, and AFM experiments. Because of the molecular design and the contribution of isolating alkyl chains to the hybrid dielectric, our devices operate at low supply voltages (-4 V to +4 V), which is a key requirement for practical use and simplifies the integration in standard applications. The monolayer devices operate in ambient air and show hole and electron mobilities of 10(-5) cm(2)/(V s) and 10(-4) cm(2)/(V s) respectively. In particular the n-type operation of self-assembled monolayer transistors has not been reported before. Hereby, structure-property relations of the SAMs have been studied. Furthermore an approach to protect the sensitive C(60) from immediate degradation within the molecular design is provided.     

Electronic behaviour of iron ions at copper sites

The electronic properties of the ceramic superconductor Y-Ba-Cu-Fe-O system with different amounts of iron cations versus temperature are discussed. The spin fluctuations of copper and its relation to the superconducting state are discussed from the point of view of the mixed valence state of copper ions. The results suggested a spin-glass behaviour at low temperature.     

Medium effect on electrochemical behaviour of anodized aluminium

The effect of some anions on the growth of the oxide film on aluminium was studied in acid and neutral media, as well as the effect of pH in presence of the same anion. In all the cases studied an inner barrier layer is formed adjacent to the metal and is covered on top with a porous layer. This latter outer layer differentiates into two regions, the one adjacent to the solution being characterized by a more open structure and a higher degree of anion incorporation as compared to the region embedded between it and the inner barrier layer. The rate of dissolution of the barrier layer is not affected by pH or anion type prevailing in the formation medium, since this layer is formed of pure alumina. The dissolution of the outer porous layer, on the other hand, is affected by both pH and anion type.     

Molecular recognition of protonated polyamines at calix[4]crown-5 self-assembled monolayer modified electrodes by impedance measurements

Molecular recognition of protonated aliphatic polyamines has been studied at calix[4]crown-5 self-assembled monolayer modified gold electrodes by electrochemical impedance spectroscopic (EIS) experiments. The energy of complex formation between the calix [4]crown-5 molecule and a series of alkyl ammonium ions was shown by molecular modeling and EIS experiments to depend on the number of amine groups in the alkyl chain as well as the number of methylene groups between the amine groups. The structures of complexes formed between the crown ether on the lower rim of calix[4]arene and protonated amines were determined by minimizing the complex formation energies. The adducts thus formed on the SAM rendered the electron transfer from the electrode to the probe (Fe(CN)63-/4- pair) easier or more difficult depending on the number of ammonium groups and their arrangement in linear alkyl chains. Analytical procedures have been developed to detect protonated spermidine (a recognized cancer marker) in simulated urine, blood, erythrocyte, and cerebrospinal fluids.     

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.     

High-performance carbon nanotube field effect transistors with a thin gate dielectric based on a self-assembled monolayer

Individual single-walled carbon nanotube (SWCNT) field effect transistors (FETs) with a 2 nm thick silane-based organic self-assembled monolayer (SAM) gate dielectric have been manufactured. The FETs exhibit a unique combination of excellent device performance parameters. In particular, they operate with a gate-source voltage of only -1 V and exhibit good saturation, large transconductance, and small hysteresis (相似文献   

Selective electrochemical sensing of glycated hemoglobin (HbA1c) on thiophene-3-boronic acid self-assembled monolayer covered gold electrodes

We report a novel concept of sensing glycated hemoglobin, HbA 1c, which is now the most important index for a long-term average blood glucose level, by first selectively immobilizing it on the thiophene-3-boronic acid (T3BA) self-assembled monolayer (SAM)-covered gold electrode by a selective chemical reaction with boronic acid. HbA 1c thus immobilized is then detected by the label-free electrochemical impedance spectroscopic (EIS) measurements with a redox probe, an equimolar mixture of K 3Fe(CN) 6 and K 4Fe(CN) 6, present. The rate of charge transfer between the electrode and the redox probe is shown to be modulated by the amount of HbA 1c in the matrix hemoglobin solution due to the blocking effect caused by the binding of HbA 1c with boronic acid. Both the formation of a well-defined T3BA-SAM on the gold surface and the chemical binding of its boronic acid with HbA 1c in solution were confirmed by quartz crystal microbalance, atomic force microscopy, and EIS experiments.     

Electrochemical polymerization of an aniline-terminated self-assembled monolayer on indium tin oxide electrodes and its effect on polyaniline electrodeposition

Indium tin oxide (ITO) transparent electrodes were surface modified by a self-assembled monolayer of N-phenyl-γ-aminopropyl-trimethoxysilane (PAPTS). Cyclic voltammetry of the PAPTS monolayer in aniline-free aqueous electrolyte showed the typical shape of a surface-confined monomer, due to the oxidation of the aniline moieties. This process resulted in a two-dimensional polyaniline film with uniform thickness of 1.3 nm, as measured by atomic force microscopy. X-ray photoelectron and UV–visible spectroscopic techniques confirm the formation of a conjugated polymer film. The influence of the surface modification of ITO electrodes on polyaniline electrochemical deposition was also studied. The initial oxidation rate of aniline increased in the PAPTS-modified ITO electrodes, although the overall film formation rate was lower than that of unmodified ITO electrodes. The morphology of the electrodeposited polyaniline films on PAPTS-modified and unmodified ITO electrodes was studied by atomic force microscopy. Films of smaller grain were grown in the PAPTS-modified ITO as compared to films grown on unmodified ITO. A blocking effect due to the propyl spacer is proposed to explain the reduced electron transfer in PAPTS-modified electrodes.     

Nanoscale fabrication of myoglobin monolayer on self-assembled DTSSP for bioelectronic device

The fabrication method of nanoscale myoglobin monolayer using chemical linker is introduced in this study because control of amount and orientation of protein immobilized on electronic device is one of main issues to be solved for the realization of biomolecular electronic device. Myoglobin, metalloprotein, is selected as active material due to its electrochemical property. To immobilize myoglobin on Au surface, 3,3-dithiobis (sulphosuccinimidyl propionate) (DTSSP) is utilized as a chemical linker. The optimum amount of protein is investigated by surface plasmon resonance (SPR). SPR and scanning tunneling microscope (STM) results confirm the nano scale protein layer formed on DTSSP self assembled monolayer (SAM) on Au surface. Protein layer on Au surface using DTSSP as chemical linker was more stable than random adsorption without linker as aspect of redox character due to the fact that myoglobin immobilized with chemical linker did not lose its redox property after long usages.     

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.     

Tandem fourier transform mass spectrometry studies of surface-induced dissociation of benzene monomer and dimer ions on a self-assembled fluorinated alkanethiolate monolayer surface

A new instrument configuration based on a Finnigan FTMS-2000 platform has been applied to the study of surface-induced dissociation (SID) in this research. Benzene monomer ions C(6)H(6)(+) and dimer ions (C(6)H(6))(2)(+) were impacted on a fluorinated self-assembled monolayer surface at collision energies ranging from 1 to 70 eV. Benzene cations were chosen for this study because the fragmentation characteristics of the molecular cation are well known and its SID has been thoroughly investigated. SID spectra obtained by FTMS-SID are very similar to those reported in the literature for the same surface but exhibit much higher mass resolution. A comparison study of collision-induced dissociation (CID) and SID of benzene molecular cations was performed utilizing the same ICR cell and ion detection protocol. It is demonstrated that SID provides both much higher energy deposition and a narrower internal energy distribution than CID. The present instrument geometry and experimental protocol demonstrate much higher efficiencies than previous SID studies by FTMS and much higher mass resolution than previous SID studies using other types of mass analyzers.     

Natural formation of a protective layer on copper and copper brazing in domestic water: structural characterization and electrochemical behaviour

The coupling Cu/Cu-P brazing, which is that most employed in domestic water supply pipes, has been investigated. Potentiostatic corrosion experiments were performed in domestic water under different conditions. It appears that the brazing has a better resistance than copper. The nature of the films formed at the sample surfaces was determined by various analysis techniques and the thicknesses were measured by ellipsometry. It was observed that it was the difference in composition of the films, formed at copper and brazing surfaces, which allowed the Cu-P brazing to become more noble than copper. The relatively thicker film formed on brazing, appears to contain mainly calcium carbonate and sulphate which grow epitaxially on calcium phosphate (hydroxyapatite or brishite). The corrosion resistance of the studied brazing was not only related to the galvanic coupling copper/brazing, but also depended on other parameters, mainly the water-flow velocity.     

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.