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1.
Stability of self-assembled monolayers on titanium and gold   总被引:1,自引:0,他引:1  
Methyl- and hydroxyl-terminated phosphonic acid self-assembled monolayers (SAMs) were coated on Ti from aqueous solution. Dodecyl phosphate and dodecyltrichlorosilane SAMs were also coated on Ti using solution-phase deposition. The stability of SAMs on Ti was investigated in Tris-buffered saline (TBS) at 37 degrees C using X-ray photoelectron spectroscopy, contact angle goniometry, and atomic force microscopy. For comparison purposes, a hydroxyl-terminated thiol SAM was coated on Au, and its stability was also investigated under similar conditions. In TBS, a significant proportion of phosphonic acid or phosphate molecules were desorbed from the Ti surface within 1 day, while the trichlorosilane SAM on Ti or thiol SAM on Au was stable for up to 7 days under similar conditions. The stability of hydroxyl-terminated phosphonic acid SAM coated Ti and thiol SAM coated Au was investigated in ambient air and ultraviolet (UV) light. In ambient air, the phosphonic acid SAM on Ti was stable for up to 14 days, while the thiol SAM on Au was not stable for 1 day. Under UV-radiation exposure, the alkyl chains of the phosphonic acid SAM were decomposed, leaving only the phosphonate groups on the Ti surface after 12 h. Under similar conditions, decomposition of alkyl chains of the thiol SAM was observed on the Au surface accompanied by oxidation of thiolates.  相似文献   

2.
《Electroanalysis》2003,15(12):1060-1066
The voltammetric behavior of methylene blue (MB) at thiol self‐assembled monolayers modified gold electrodes (SAMs/Au) has been investigated. MB exhibited a redox peak at about ?0.35 V (vs.SCE) in alkaline solution at bare gold electrodes. When the gold electrodes were modified with thiol SAMs, the peak grew due to the accumulation of MB at SAMs. With the solution pH rising, more MB was accumulated, hence the peak height increased, which differed from that at bare gold electrodes. The electrode process at SAMs/Au featured the characteristics of adsorption and/or electrode reaction controlled. The enhancing action of glutathione monolayer (GSH SAM), 3‐mercaptopropionic acid monolayer (3MPA SAM) and other thiol SAMs was compared. Among these, GSH SAM made the MB peak increase more. At GSH SAM/Au, the peak height varied linearly with MB concentration over the range of 2 μM to 400 μM. So this can be developed for the determination of MB and studies concerned. The accumulation behavior caused by GSH SAM and native fish sperm dsDNA was compared. The interaction between DNA and MB was also discussed under this condition.  相似文献   

3.
The adsorption pattern of gold nanoparticles (AuNPs) on functionalized self-assembled monolayers (SAMs) produced on a Au(111) surface was characterized. The Au(111) was modified with 11-amino-1-undecanethiol hydrochloride (AUT), 11-mercapto-1-undecanol (MUT), or 11-mercaptoundecanoic acid (MUA) at an elevated temperature and pressure. The AuNPs aggregated on the AUT-SAM surface, whereas they were well dispersed on the MUT-SAM surface and localized on the MUA-SAM surface. The results suggest that interactions between AuNPs differ according to the degree of peeling of citrate-layer-capped AuNPs. The degree of peeling, which is related to both the surface randomness of the SAMs and the functional characteristics of the terminal group of each SAM, was discussed on the basis of scanning tunneling microscopy observations, X-ray photoelectron spectroscopic analyses, and contact angle measurements. Our study shows that AuNP patterns can be controlled by changing the terminal group of the alkyl thiol SAM on a Au(111) surface.  相似文献   

4.
Characterization of single- and double-stranded DNA on gold surfaces   总被引:2,自引:0,他引:2  
Single- and double-stranded deoxy ribonucleic acid (DNA) molecules attached to self-assembled monolayers (SAMs) on gold surfaces were characterized by a number of optical and electronic spectroscopic techniques. The DNA-modified gold surfaces were prepared through the self-assembly of 6-mercapto-1-hexanol and 5'-C(6)H(12)SH -modified single-stranded DNA (ssDNA). Upon hybridization of the surface-bound probe ssDNA with its complimentary target, formation of double-stranded DNA (dsDNA) on the gold surface is observed and in a competing process, probe ssDNA is desorbed from the gold surface. The competition between hybridization of ssDNA with its complimentary target and ssDNA probe desorption from the gold surface has been investigated in this paper using X-ray photoelectron spectroscopy, chronocoulometry, fluorescence, and polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS). The formation of dsDNA on the surface was identified by PM-IRRAS by a dsDNA IR signature at approximately 1678 cm(-)(1) that was confirmed by density functional theory calculations of the nucleotides and the nucleotides' base pairs. The presence of dsDNA through the specific DNA hybridization was additionally confirmed by atomic force microscopy through colloidal gold nanoparticle labeling of the target ssDNA. Using these methods, strand loss was observed even for DNA hybridization performed at 25 degrees C for the DNA monolayers studied here consisting of attachment to the gold surfaces by single Au-S bonds. This finding has significant consequence for the application of SAM technology in the detection of oligonucleotide hybridization on gold surfaces.  相似文献   

5.
Self-assembled monolayers (SAMs) were formed by the spontaneous adsorption of octythiocyanate (OTC) on Au(111) using both solution and ambient-pressure vapor deposition methods at room temperature and 50 degrees C. The surface structures and adsorption characteristics of the OTC SAMs on Au(111) were characterized by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The STM observation showed that OTC SAMs formed in solution at room temperature have unique surface structures including the formation of ordered and disordered domains, vacancy islands, and structural defects. Moreover, we revealed for the first time that the adsorption of OTC on Au(111) in solution at 50 degrees C led to the formation of SAMs containing small ordered domains, whereas the SAMs formed by vapor deposition at 50 degrees C had long-range ordered domains, which can be described as (radical3 x 2 radical19)R5 degrees structures. XPS measurements of the peaks in the S 2p and N 1s regions for the OTC SAMs showed that vapor deposition is the more effective method as compared to solution deposition for obtaining high-quality SAMs by adsorption of OTC on gold. The results obtained will be very useful in understanding the SAM formation of organic thiocyanates on gold surfaces.  相似文献   

6.
Characterization of self-assembled monolayers of thiols on Au(111)   总被引:1,自引:0,他引:1  
Self-assembled monolayers (SAMs) of n-butanethiol, n-dodecanethiol and their equimolar mixture on Au(111) were prepared and characterized by ellipsometry, contact angle measurement, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results revealed that these SAMs are oriented ultrathin films with the thickness of nanometer scale, and the SAMs were influenced by the molecular chain length, the lattice orientation and cleanliness of the substrates. The surface of the longer chain SAM is hydrophobic. The thicknesses of three SAMs of n-butanethiol, n-dodecanethiol and their mixture revealed by ellipsometry and XPS are about 0.59 - 0.67nm, 1.60- 1.69 nm and 1.23 - 1.32nm, respectively. AFM images further demonstrated that the SAM formed by the mixture has some microdomains with two different thicknesses.  相似文献   

7.
This study demonstrated that the work function (Φ) of Au substrates can be fine-tuned by using series ratios of binary self-assembled monolayers (SAMs). By using pure amine- and carboxylic acid-bearing alkanethiol SAM on gold substrates, Φ of Au changed from 5.10 to 5.16 and 5.83, respectively, as determined by ultra-violet photoelectron spectrometry (UPS). The shift in Φ due to the use of different functional groups was rationalized by considering the dipole moments of the molecules anchored on the Au surface. A series of binary SAMs were fabricated by mixing carboxylic acid- and amine-terminated alkanethiols in the deposition solution. By mixing these functional groups in SAMs, a linear correlation between Φ with respect to chemical composition (hence the effective dipole moment on the Au surface) was observed. It was found that arbitrary Φ between extremes (5.16 and 5.83) controlled by respective functional groups can be obtained by changing the chemical composition of SAMs. The Scanning Kelvin Probe (SKP) was also used to measure the contact potential difference (CPD) between SAMs and referencing Au on a patterned substrate prepared by photo-lithography. It was found that the CPD of SAMs with different chemical compositions correlates to their Φ. However, the magnitude of the CPD was smaller than the difference in Φ measured by UPS that was possibly due to the adsorption of contaminants in air.  相似文献   

8.
The fabrication of enzyme electrodes using self-assembled monolayers (SAMs) has attracted considerable interest because of the spatial control over the enzyme immobilization. A model system of glucose oxidase covalently bound to a gold electrode modified with a SAM of 3-mercaptopropionic acid was investigated with regard to the effect of fabrication variables such as the surface topography of the underlying gold electrode, the conditions during covalent attachment of the enzyme and the buffer used. The resultant monolayer enzyme electrodes have excellent sensitivity and dynamic range which can easily be adjusted by controlling the amount of enzyme immobilized. The major drawback of such electrodes is the response which is limited by the kinetics of the enzyme rather than mass transport of substrates. Approaches to bringing such enzyme electrodes into the mass transport limiting regime by exploiting direct electron transfer between the enzyme and the electrode are outlined.  相似文献   

9.
We report the immobilization of gold nanorods onto self-assembled monolayers (SAMs) of 16-mercaptohexadecanoic acid (16-MHA). The simple two step protocol involves formation of a SAM of 16-MHA molecules onto gold-coated glass slides and subsequent immersion of these slides into the gold nanorod solution. The nanorods, formed by a seed-mediated, surfactant-assisted synthesis protocol, are stabilized in solution due to surface modification by the surfactant cetyltrimethylammonium bromide (CTAB). Attractive electrostatic interactions between the carboxylic acid group on the SAM and the positively charged CTAB molecules are likely responsible for the nanorod immobilization. UV-vis spectroscopy has been used to follow the kinetics of the nanorod immobilization. The nature of interaction between the gold nanorods and the 16-MHA SAM has been probed by Fourier transform infrared spectroscopy (FTIR). The surface morphology of the immobilized rods is studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements. SEM was also used to determine the density of the immobilized nanorods as a function of the pH of immobilization. Control over the surface coverage of the immobilized gold nanorods has been demonstrated by simple pH variation. Such well-dispersed immobilized gold nanorods with control over the surface coverage could be interesting substrates for applications such as surface-enhanced Raman spectroscopy (SERS).  相似文献   

10.
We have investigated the reaction of tetrakis(dimethylamido)titanium, Ti[N(CH(3))(2)](4), with N-isopropyl-N-[4-(thien-3-ylethynyl) phenyl] amine and N-isopropyl-N-(4-{[4-(thien-3-ylethynyl) phenyl]ethynyl}phenyl) amine self-assembled monolayers (SAMs), on polycrystalline Au substrates. The structure of the SAMs themselves has also been investigated. Both molecules form SAMs on polycrystalline Au bound by the thiophene group. The longer-molecular-backbone molecule forms a denser SAM, with molecules characterized by a smaller tilt angle. X-ray photoelectron spectroscopy (XPS) and angle-resolved XPS have been employed to examine the kinetics of adsorption, the spatial extent of reaction, and the stoichiometry of reaction. For both the SAMs, adsorption is described well by first-order Langmuirian kinetics, and adsorption is self-limiting from T(s) = -50 to 30 degrees C. The use of angle-resolved XPS clearly demonstrates that the Ti[N(CH(3))(2)](4) reacts exclusively with the isopropylamine end group via ligand exchange, and there is no penetration of the SAM, followed by reaction at the SAM-Au interface. Moreover, the SAM molecules remain bound to the Au surface via their thiopene functionalites. From XPS, we have found that, in both cases, approximately one Ti[N(CH(3))(2)](4) is adsorbed per two SAM molecules.  相似文献   

11.
Arya SK  Pandey P  Singh SP  Datta M  Malhotra BD 《The Analyst》2007,132(10):1005-1009
A dithiobissuccinimidyl propionate (DTSP) self-assembled monolayer (SAM) prepared onto a gold (Au) surface has been utilized for covalent immobilization of cholesterol oxidase (ChOx) and cholesterol esterase (ChEt). These ChOx-ChEt/DTSP/Au bio-electrodes have been characterized using electrochemical impedance and cyclic voltammetric (CV) techniques, respectively. Differential pulse voltammetry (DPV) has been used for enzymatic assay of immobilized ChOx and ChEt onto the DTSP modified gold surface as a function of cholesterol oleate concentration. The response measurement conducted on ChOx-ChEt/DTSP/Au bio-electrode reveal the value of Michaelis-Menten constant (Km) as 0.95 mM suggesting enhanced affinity of enzymes (ChOx and ChEt). The ChOx-ChEt/DTSP/Au bio-electrodes show linearity in range of 50 to 400 mg dl(-1) of cholesterol oleate and the shelf-life of more than 50 days when stored at 4 degrees C. This biosensing electrode shows correlation coefficient of 0.9973 and standard deviation of regression as 0.859 microA.  相似文献   

12.
Self-assembled monolayers (SAMs) of 4,4'-thiobisbenzenethiol (TBBT) can be formed on Au surface spontaneously. The structural characteristics and adsorption behavior of TBBT SAMs on Au have been investigated by surface enhanced Raman scattering (SERS), electrochemical cyclic voltammetry (CV), ac impedance spectroscopy (EIS), and atomic force microscopy (AFM). It is demonstrated that TBBT adsorbed on Au by losing a H atom, forming one Au-S bond, and the other mercapto group is free at the surface of the monolayer owing to the presence of the nu(S-H) at 2513 cm(-1) and the delta(C-S-H) at 910 cm(-1) in SERS. The enhancement of the vibration of C-S (1064 cm(-1)), the aromatic C-H vibration (3044 cm(-1)), and the absence of the vibration of S-S illustrate TBBT adsorbed on Au forming a monolayer with one benzene ring tilted with respect to the Au surface. The interpretation of the observed frequencies is aided by ab initio molecular orbital (MO) calculations at the HF/6-31G level of theory. Electrochemical CV and EIS indicate TBBT monolayers can passivate the Au effectively for its low ratio of pinhole defects (theta = 99.6%). AFM studies give details about the surface morphology. The applications of TBBT SAMs have been extensively investigated by exposure of Cu2+ ion to TBBT SAMs on Au and covalent adsorption of metal nanoparticles. Electrochemical, X-ray photoelectron spectroscopic, and SERS results indicate that Cu2+ can react with TBBT SAMs and present on TBBT SAMs as Cu(I). A scanning electron microscopic image of Ag nanoparticles on TBBT/Au and the Raman spectrum of TBBT in smooth macroscopic Au/TBBT SAMs/Ag nanoparticle sandwich structure indicate that metal nanoparticles can be adsorbed on TBBT SAMs effectively through covalent linkage.  相似文献   

13.
Soft landing of mass-selected peptide ions onto reactive self-assembled monolayer surfaces (SAMs) was performed using a newly constructed ion deposition apparatus. SAM surfaces before and after soft landing were characterized ex situ using time-of-flight secondary-ion mass spectrometry (TOF-SIMS) and infrared reflection-absorption spectroscopy (IRRAS). We demonstrate that reactive landing (RL) results in efficient covalent linking of lysine-containing peptides onto the SAM of N-hydroxysuccinimidyl ester-terminated alkylthiol on gold (NHS-SAM). Systematic studies of the factors that affect the efficiency of RL revealed that the reaction takes place upon collision and is promoted by the kinetic energy of the ion. The efficiency of RL is maximized at ca. 40 eV collision energy. At high collision energies the RL efficiency decreases because of the competition with scattering of ions off the surface. The reaction yield is independent of the charge state of the projectile ions, suggesting that peptide ions undergo efficient neutralization upon collision. Chemical and physical properties of the SAM surface are also important factors that affect the outcome of RL. The presence of chemically reactive functional groups on the SAM surface significantly improves the reaction efficiency. RL of mass- and energy-selected peptide ions on surfaces provides a highly specific approach for covalent immobilization of biological molecules onto SAM surfaces.  相似文献   

14.
灿烂甲酚蓝在DNA修饰金电极上的电化学行为   总被引:1,自引:0,他引:1  
利用自组装技术将巯基乙醇固定在金电极表面形成巯基乙醇自组装膜修饰金电极, 用乙基-(3-二甲基氨丙基)碳二亚胺盐酸盐(EDC)和N-羟基琥珀酰亚胺(NHS)为偶联试剂, 分别将鲱鱼精单链DNA(ssDNA)和双链DNA(dsDNA)固定于金电极表面形成ssDNA和dsDNA 修饰电极. 考察了灿烂甲酚蓝(BCB)在不同DNA 修饰电极上的电化学行为,结果表明, BCB 在ssDNA 和dsDNA 修饰电极上的吸附常数分别为1.67×10^4和3.22×10^4 L·mol-1, BCB 与ssDNA 主要以静电作用结合, 而与dsDNA作用存在静电和嵌插两种模式. dsDNA 对BCB 具有更高的亲和力, 使BCB 可以作为一种有效的电化学杂交指示剂.  相似文献   

15.
One of the sulfobetaine methacrylate (SBMA) monomers, N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine, was polymerized onto initiator-covered gold surfaces using atom transfer radical polymerization (ATRP) to form uniform polymer brushes. Self-assembled monolayers (SAMs) with ATRP initiators were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The thickness of grafted poly(SBMA) films was measured by ellipsometry. Fibrinogen adsorption on poly(SBMA) grafted surfaces was measured with a surface plasmon resonance (SPR) sensor. Two approaches were compared to graft ATRP initiators onto gold surfaces for surface polymerization and subsequent protein adsorption on these polymer grafted surfaces. The first was to prepare a SAM from omega-mercaptoundecyl bromoisobutyrate onto a gold surface. Superlow fouling surfaces with well-controlled poly(SBMA) brushes were achieved using this approach (e.g., fibrinogen adsorption <0.3 ng/cm2). The second approach was to react bromoisobutyryl bromide with a hydroxyl-terminated SAM on a gold surface. Although protein adsorption decreased as the density of surface initiators increased, the surface prepared using the second approach was not able to achieve as low protein adsorption as the first approach. Key parameters to achieve superlow fouling surfaces were studied and discussed.  相似文献   

16.
Adsorption of water on self-assembled monolayers (SAMs) of 4-(4-mercaptophenyl)pyridine on gold at low temperatures under ultrahigh vacuum conditions is studied by synchrotron radiation X-ray photoelectron and absorption spectroscopy. Water adsorption induces a strong modification of the chemical state of the pyridine N atoms at the SAM/ice interface, indicative for strong H bonding and partial proton transfer between water molecules and pyridine moieties. Additionally, the initial molecular orientation within the SAM is changed upon formation of an adsorbed water multilayer.  相似文献   

17.
The immobilization of surface-derivatized gold nanoparticles onto methyl-terminated self-assembled monolayers (SAMs) on gold surface was achieved by the cooperation of hydrophobic and electrophoretic forces. Electrochemical and scanning probe microscopy techniques were utilized to explore the influence of the SAM's structure and properties of the nanoparticle/SAM/gold system. SAMs prepared from 1-decanethiol (DT) and 2-mercapto-3-n-octylthiophene (MOT) were used as hydrophobic substrates. The DT SAM is a closely packed and organized monolayer, which can effectively block the underlying gold and inhibit a variety of solution species including organic and inorganic molecules from penetrating, whereas the MOT monolayer is poorly packed or disorganized (because of a large difference in dimension between the thiophene head and the alkylchain tail) and permeable to many organic probes in aqueous solution but not to inorganic probes. Thus, the MOT monolayer provides a more energetically favorable hydrophobic surface for the penetration and adsorption of organic species than the DT monolayer. This hypothesis is supported by experiments in which the density of hydrophobically immobilized nanoparticles on the MOT SAM is much larger than that on the DT SAM. The results also suggest new approaches for modification of macroscopic surfaces with nanoscopic particles.  相似文献   

18.
We report a simple, universal method for forming high surface coverage SAMs on ferromagnetic thin (< or =100 nm) films of Ni, Co, and Fe. Unlike previous reports, our technique is broadly applicable to different types of SAMs and surface types. Our data constitutes the first comprehensive examination of SAM formation on three different ferromagnetic surface types using two different surface-binding chemistries (thiol and isocyanide) under three different preparation conditions: (1) SAM formation on electroreduced films using a newly developed electroreduction approach, (2) SAM formation on freshly evaporated surfaces in the glovebox, and (3) SAM formation on films exposed to atmospheric conditions beforehand. The extent of SAM formation for all three conditions was probed by cyclic voltammetry for surfaces functionalized with either (11-thiolundecyl)ferrocene (Fc-(CH2) 11-SH) or (11-isocyanoundecyl)ferrocene (Fc-(CH2) 11-NC). SAM formation was also probed for straight-chain molecules, hexadecanethiol and hexadecaneisocyanide, with contact angle measurements, X-ray photoelectron spectroscopy, and reflection-absorption infrared spectroscopy (RAIRS). The results show that high surface coverage SAMs with low surface-oxide content can be achieved for thin, evaporated Ni and Co films using our electroreduction process with thiols. The extent of SAM formation on electroreduced films is comparable to what has been observed for SAMs/Au and to what we observe for SAMs/Ni, Co, and Fe samples prepared in the glovebox.  相似文献   

19.
This paper presents a novel method for preparing aromatic, mixed self-assembled monolayers (SAMs) with a dilute surface fraction coverage of protonated amine via in situ hydrolysis of C═N double bond on gold surface. Two imine compounds, (4'-(4-(trifluoromethyl)benzylideneamino)biphenyl-4-yl)methanethiol (CF(3)-C(6)H(4)-CH═N-C(6)H(4)-C(6)H(4)-CH(2)-SH, TFBABPMT) and (4'-(4-cyanobenzylideneamino)biphenyl-4-yl)methanethiol (CN-C(6)H(4)-CH═N-C(6)H(4)-C(6)H(4)-CH(2)-SH, CBABPMT), self-assembled on Au(111) to form highly ordered monolayers, which was demonstrated by infrared reflection absorption spectroscopy (IRRAS) and X-ray photoelectron spectroscopy (XPS). A nearly upright molecular orientation for CF(3)- and CN-terminated SAM was detected by near edge X-ray absorption fine structure (NEXAFS) measurements. Afterward, the acidic catalyzed hydrolysis was carried out in chloroform or an aqueous solution of acetic acid (pH = 3). Systematic studies of this hydrolysis process for CN-terminated SAM in acetic acid at 25 °C were performed by NEXAFS measurements. It was found that about 30% of the imine double bonds gradually cleaved in the first 40 min. Subsequently, a larger hydrolysis rate was observed due to the freer penetration of acetic acid in the SAM and resultant more open molecular packing. Furthermore, the molecular orientation in mixed SAMs did not change during the whole hydrolysis process. This partially hydrolyzed surface contains a controlled amount of free amines/ammonium ions which can be used for further chemical modifications.  相似文献   

20.
Binary mixtures of 11-mercaptoundecanoic acid (MUA) and other thiols of various lengths and terminal functions were chemisorbed on gold-coated surfaces via S–Au bonds to form mixed self-assembled monolayers (SAMs). Several values of the mole fraction of MUA in the thiol mixtures were tested and the structure and composition of the resulted thin films were characterized by X-ray photoelectron spectroscopy (XPS) and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). The results made it clear that co-adsorption of MUA with thiols of similar chain length led to well-ordered monolayers whereas the co-adsorption of MUA with shorter thiols yielded less crystalline-like thin films, but with more reactive carboxylic acid terminal groups. This criterion appeared decisive for efficient covalent binding of Staphylococcus aureus Protein A (PrA), a protein that displays high affinity for the constant fragment (Fc) of antibodies of the IgG type from various mammal species. The ability of immobilized Protein A to recognize and bind a model IgG appeared to be optimal for the mixed SAM of MUA and the short-chain, ω-hydroxythiol 6-mercaptohexanol in the proportion 1–3.  相似文献   

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