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1.
The kinetics of the adsorption of metal ions onto a thiolated surface and the selective and quantitative sensing of metal ions were explored using surface plasmon resonance (SPR) spectroscopy. The target metal ion was an aqueous solution of Pt2+ and a thin-gold-film-coated glass substrate was modified with 1,6-hexanedithiol (HDT) as a selective sensing layer. SPR spectroscopy was used to examine the kinetics of metal ion adsorption by means of the change in SPR angle. The selectivity of the thiolated surface for Pt2+ over other divalent metal ions such as Cu2+, Ni2+, and Cd2+ was evident by the time-resolved SPR measurement. SPR angle shift, deltatheta(SPR), was found to increase logarithmically with increasing concentration of Pt2+ in the range of 1.0 x 10(-5)-1.0 mM. The rate of Pt2+ adsorption on HDT observed at both 0.1 and 1 mM Pt2+ accelerates until the surface coverage reaches approximately 17%, after which the adsorption profile follows Langmuirian behavior with the surface coverage. The experimental data indicated that heavy metal ions were adsorbed to the hydrophobic thiolated surface by a cooperative mechanism. A mixed self-assembled monolayer (SAM) composed of HDT and 11-mercaptoundecanoic acid was used to reduce the hydrophobicity of the thiol-functionalized surface. The addition of hydrophilic groups to the surface enhanced the rate of adsorption of Pt2+ onto the surface. The findings show that the adsorption of metal ions is strongly dependent upon the hydrophilicity/hydrophobicity of the surface and that the technique represents an easy method for analyzing the adsorption of metal ions to a functionalized surface by combining SPR spectroscopy with a SAM modification.  相似文献   

2.
This work describes a comparative study between two biosensing platforms that are commonly used to immobilize capture probes. These platforms refer to thiolated and biotinylated oligonucleotide strands chemisorbed on Au surfaces (DNA SAM) and bioconjugated on streptavidin (SA) monolayers (SA SAM), respectively. Both interfacial architectures were studied using surface acoustic wave (SAW) devices and surface plasmon spectroscopy (SPR). Our studies indicated that DNA SAM platforms enable higher densities of surface-confined oligonucleotide probes. However, their hybridization efficiency is lower when compared to that obtained in SA SAM platforms, thus impacting on a lower detection limit, 5 nM. Furthermore, binding of SA molecules to the biotinylated targets, in an attempt to enhance the signal in both platforms, revealed striking differences between both architectures. The SA underlayer used in the SA SAM configuration confers nonfouling characteristics to the interfacial assembly, thus precluding the nonspecific binding of SA onto the surface. The antifouling behavior of the SA DNA platform is an important feature to be considered in the amplification of hybridization events through the bioconjugation of biotinylated targets with streptavidin-based tags.  相似文献   

3.
The redox-induced assembly of amphiphilic molecules and macromolecules at electrode surfaces is a potentially attractive means of electrochemically modulating the organization of materials and nanostructures on solid substrates via ion-pairing interactions or charge-transfer complexation. In this regard, we have investigated the potential-induced adsorption and aggregation of dodecyl sulfate, a common anionic surfactant, at a ferrocenylundecanethiolate (FcC11SAu) self-assembled monolayer (SAM)/aqueous solution interface by electrochemical surface plasmon resonance (ESPR) spectroscopy. The surfactant anions adsorb onto the electroactive SAM by specific ion-pairing interactions with the oxidized ferricinium species. The ferricinium charge density (QFc+) obtained by cyclic voltammetry and surface coverage measured by SPR indicate that the dodecyl sulfate forms an interdigitated monolayer, where half of the surfactant molecules have their sulfate headgroups paired to the surface and half have their headgroups exposed to the aqueous solution. The surface coverage of dodecyl sulfate was found to depend on both the ferricinium surface concentration and the surfactant aggregation state in solution. A maximum coverage of dodecyl sulfate on the ferricinium surface is obtained below the critical micelle concentration (cmc), in contrast to dodecyl sulfate adsorption to SAM surfaces of static positive charge. This marked difference in adsorption behavior is attributed to the dynamic generation of ferricinium by potential cycling and the specific nature of the ion-pairing interactions versus pure electrostatic ones. The results presented point to a new way of organizing molecules via electrical stimulus.  相似文献   

4.
An electroactive self-assembled monolayer (SAM) was fabricated by covalent attachment of a novel hydroquinone-terminated dodecanethiol onto the gold surface and its electrochemical behavior was investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The capability of the designed SAM in immobilization of organic molecules onto the gold surface was studied utilizing the Michael-addition as a model reaction. The results obtained from cyclic voltammetry, electrochemical impedance and grazing incidence Fourier transform infrared (GI-FTIR) spectroscopy revealed that, upon applying an anodic potential to the Au-SAM electrode system in the presence of glutathione, the electrochemically generated p-quinone participated in a Michael-addition reaction with glutathione and the corresponding Michael adduct was formed at the solid–liquid interface. The kinetic parameters were then derived for this interfacial Michael-addition reaction.  相似文献   

5.
Heparin was covalently immobilized onto a silicon surface by two different methods, carbodiimide-based immobilization and photo-immobilization. In the former method, a (3-aminopropyl) trimethoxysilane (APTMS) self-assembled monolayer (SAM) or multilayer was first coated onto the silicon surface as the bridging layer, and heparin was then attached to the surface in the presence of water-soluble carbodiimide. In the latter method, an octadecyltrichlorosilane (OTS) SAM was coated on the silicon surface as the bridging layer, and heparin was modified by attaching photosensitive aryl azide groups. Upon UV illumination, the modified heparin was then covalently immobilized onto the surface. The hydrophilicity of the silicon surface changed after each coating step, and heparin aggregates on APTMS SAM and OTS SAM were observed by atomic force microscopy (AFM). In vitro haemocompatibility assays demonstrated that the deposition of APTMS SAM, APTMS multilayer and OTS SAM enhanced the silicon's haemocompatibility, which was further enhanced by the heparin immobilization. There is no evident distinction regarding the haemocompatibility between the heparin-immobilized surfaces by both methods. However, heparin on silicon with APTMS SAM and multilayer as the bridging layers is very unstable when tested in vitro with a saline solution at 37 °C, due to the instability of APTMS SAM and multilayer on silicon. Meanwhile, photo-immobilized heparin on silicon with OTS SAM as the bridging layer showed superb stability.  相似文献   

6.
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   

7.
Soft- and reactive-landing of gas-phase synthesized cationic Cr(aniline)(2) complexes onto self-assembled monolayers of methyl-terminated (CH(3)-SAM) and carboxyl-terminated (COOH-SAM) organothiolates coated on gold were performed at hyperthermal collision energy (5-20 eV). The properties of the Cr(aniline)(2) complexes on the SAM surfaces were characterized using infrared reflection absorption spectroscopy (IRAS) and temperature-programmed desorption (TPD), together with theoretical calculations based on density functional theory (DFT). For the CH(3)-SAM, the Cr(aniline)(2) complexes were embedded inside the SAM matrix in a neutral charge state, keeping a sandwich structure. For the COOH-SAM, the IRAS and TPD study revealed that the amine-containing Cr(aniline)(2) complexes were bound to the SAM surface in two forms of physisorption and chemical linking through an amide bond. In the desorption, the latter form appeared as the reaction product between organothiolates and Cr(aniline)(2) above 400 K, where the organothiolate molecules, forming the SAM, were desorbed from the gold surface. The results show that the hyperthermal depositions onto a COOH-SAM bring about reactive-landing followed by covalent linking of an amide bond between the amine-containing Cr(aniline)(2) complexes to the carboxyl-terminated SAM surface, in which the binding sites can be separated from the functional sites of the d-π interaction.  相似文献   

8.
The behavior of C(60) molecules deposited onto 11-phenoxyundecanethiol (phenoxy) self-assembled monolayers (SAMs) is studied using ultrahigh vacuum scanning tunneling microscopy (UHV-STM) and spectroscopy. We observe that after thermally annealing between 350 and 400 K in vacuum a combination of hexagonally close-packed islands, rectangularly packed islands, and isolated single lines of C(60) is observed when the C(60) is initially deposited on an unannealed phenoxy SAM. However, only rectangularly packed islands are found when they are deposited on a preannealed phenoxy SAM. We determine the rectangular packing to have a (2√3 × 4) rectangular unit cell with respect to the underlying Au(111) substrate. This type of C(60) structure has not been observed previously for multicomponent self-assemblies on a surface. We discuss the possible causes for the formation of this structure as well as the differences between starting on an unannealed SAM and an annealed one. This study demonstrates the capability of functionalized alkanethiol SAMs to control the growth and structure of C(60) islands during annealing depending on the structural changes of the SAM itself; by preannealing the SAM, the motion of the C(60) can be confined and unique structures resulting from interactions between the SAM molecules and C(60) can be produced.  相似文献   

9.
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   

10.
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   

11.
Photolithographic attachment of functional organic molecules via ester or amide linkages to self-assembled monolayers (SAMs) on gold thin films was achieved by employing a novel photoreactive surface anchor, 7-diazomethylcarbonyl-2,4,9-trithiaadmantane. The photoreactive SAM was prepared by the spontaneous physical adsorption of the photoreactive surface anchor onto gold surfaces. The alpha-diazo ketone moiety of the SAM was found to display the classical Wolff rearrangement reactivity to produce a ketene intermediate on the exposed area. Organic molecules such as alcohols and amines can thus be attached to the gold surfaces selectively by the facile in situ formation of ester or amide linkages. The structure and reactivity of the photoreactive surface anchor were characterized by real-time FT-IR, fluorescence, and polarization modulation infrared reflectance absorption spectroscopy (PM-IRRAS). The Wolff rearrangement reactivity of the SAM suggested that a "surface-isolated" carbonylcarbene may be generated when the SAM was exposed to 255-nm irradiation.  相似文献   

12.
The combination of in situ X-ray photoelectron spectroscopy, infrared reflection spectroscopy, atomic force microscopy, and time-of-flight secondary ion mass spectrometry are used to probe the nature of the evolving interface chemistry and metal morphology arising from Ti vapor deposition onto the surface of a CH(3)(CH(2))(15)S/Au{111} self-assembled monolayer (SAM) at ambient temperature. The results show that for a deposition rate of approximately 0.15 Ti atom.nm(-2).s(-1) a highly nonuniform Ti overlayer is produced via a process in which a large fraction of impinging Ti atoms do not stick to the bare SAM surface. The adsorbed atoms form isolated Ti clusters and react with CH(3) groups to form carbide products at the cluster-SAM interfaces. Further growth of Ti clusters appears to be concentrated at these scattered reaction centers. The SAM molecules in the local vicinity are subsequently degraded to inorganic products, progressing deeper into the monolayer as the deposition proceeds to give an inorganic/organic nanocomposite. A continuous overlayer does not form until metal coverage approaches approximately 50 Ti atoms per SAM molecule. These data indicate that for applications such as molecular device contacts the use of Ti may be highly problematic, suffering from both a highly nonuniform contact area and the presence of extensive inorganic products such as nonstoichiometric carbides and hydrides.  相似文献   

13.
The surface stress induced during the formation of alkanethiol self-assembled monolayers (SAMs) on gold from the vapor phase was measured using a micromechanical cantilever-based chemical sensor. Simultaneous in situ thickness measurements were carried out using ellipsometry. Ex situ scanning tunneling microscopy was performed in air to ascertain the final monolayer structure. The evolution of the surface stress induced during coverage-dependent structural phase transitions reveals features not apparent in average ellipsometric thickness measurements. These results show that both the kinetics of SAM formation and the resulting SAM structure are strongly influenced both by the surface structure of the underlying gold substrate and by the impingement rate of the alkanethiol onto the gold surface. In particular, the adsorption onto gold surfaces having large, flat grains produces high-quality self-assembled monolayers. An induced compressive surface stress of 15.9 +/- 0.6 N/m results when a c(4x2) dodecanethiol SAM forms on gold. However, the SAMs formed on small-grained gold are incomplete and an induced surface stress of only 0.51 +/- 0.02 N/m results. The progression to a fully formed SAM whose alkyl chains adopt a vertical (standing-up) orientation is clearly inhibited in the case of a small-grained gold substrate and is promoted in the case of a large-grained gold substrate.  相似文献   

14.
Gas-phase synthesized vanadium-benzene 1:2 (VBz(2)) sandwich clusters were size-selectively deposited onto bare gold and long-chain n-alkanethiolate [-S-(CH(2))(n-1)-CH(3); n = 16, 18, and 22] self-assembled monolayer (SAM)-coated gold substrates under ultrahigh vacuum (UHV) conditions. Investigation of the resulting deposited clusters was performed by infrared reflection absorption spectroscopy (IRAS) and thermal desorption spectroscopy (TDS). The IR frequencies of the soft-landed VBz(2) clusters show excellent agreement with the fundamentals reported in IR data of VBz(2) in an argon matrix. The analysis of IRAS spectra reveals that while there was no orientational preference of the VBz(2) clusters on a bare gold substrate, the VBz(2) clusters deposited onto the SAM substrates were highly oriented with the molecular axis 70-80 degrees tilted off the surface normal. In addition, analysis of TDS spectra revealed unusually large adsorption heats of the physisorbed VBz(2) clusters. The present results are explained by cluster penetration into the long-chain alkanethiolate SAM and for the first time demonstrate the matrix isolation of gas-phase organometallic clusters around room temperature.  相似文献   

15.
Metal overlayers deposited in vacuum onto self-assembled monolayer (SAM) systems serve as models for more complex metalized polymers. Metals (M) deposited onto SAMs with different organic functional end groups exhibit a wide range of behavior, ranging from strong chemical interactions with the end group to complete penetration of the metal through the SAM. In this work, we have characterized the interactions of Cu with the ---COOH of mercaptohexadecanoic acid (MHA, HOOC(CH2)15SH) SAMs self assembled on gold films by using X-ray photoelectron spectroscopy (XPS) to examine the chemical interactions, and a combination of XPS and ion scattering spectroscopy (ISS) to deduce the growth mode and penetration rate of the deposited Cu. We found that submonolayer amounts of Cu react with HOOC, whereas the rest of the Cu remains metallic and penetrates beneath the SAM surface to the SAM  Au interface. Considerable amounts of Cu (5 nm or more) will penetrate beneath the SAM layer, which is ca. 2.5 nm thick, despite the submonolayer presence of Cu at the SAM surface. The penetration rate depends strongly on the Cu deposition rate. Depositing copper onto MHA at 220 K or less, or using faster Cu deposition rates, results in slower or even completely suppressed penetration of the Cu through the SAM layer, whereas exposure to X-rays greatly enhances the penetration rate of large amounts of Cu through the SAM layer. The reacted copper is, based on the XPS 2p and LMM peaks, in the +2 oxidation state, but cannot be identified with a simple, stoichiometric oxide such as Cu2O, CuO, or Cu (OH)2.  相似文献   

16.
A monocarboxylic substituted polychlorotriphenylmethyl radical (PTMCOOH) has been grafted onto a COOH-functionalized SAM (mercaptohexadecanoic acid, MHDA SAM), using copper (II) metal ions as linkers between the carboxyl groups of the SAM and the ligand. The metal-radical adlayer has been characterized thoroughly using different surface analysis techniques, such as contact angle, IRRAS, XPS, SPR, ToF-SIMS, SFM, and NEXAFS. The magnetic character was confirmed by EPR. The density of unoccupied states was investigated using X-ray absorption spectroscopy. A low-energy peak in the NEXAFS spectrum directly revealed the presence of partially occupied electronic levels, thus proving the open-shell character of the grafted ligands. SEM measurements on a laterally patterned sample prepared by muCP of MHDA in a matrix of hexadecane thiolate (a CH 3-terminated SAM) was performed to demonstrate that the metal-assisted anchoring of the open-shell ligand occurs selectively on the COOH terminated SAM. These results represent an easy and new approach to anchor organic radicals on surfaces and constitute a first step toward the growth of magnetic metal-organic radical-based frameworks on solid substrates.  相似文献   

17.
Buckminster fullerene C60 was used as a model to understand the attachment chemistry of large molecules on amine-terminated self-assembled monolayers (SAM) on semiconductor substrates. This type of interface serves as a prototype for future devices in such fields as solar energy conversion, biosensing, catalysis, and molecular electronics. Fullerene C60 was attached to 11-amino-1-undecene self-assembled monolayers on a Si(111) surface. The chemical state and topography of the C60-modified surface were characterized by surface analytical spectroscopic and microscopic methods and by computational investigation. X-ray photoelectron spectroscopy revealed that the secondary amine group is formed between the C60 and the 11-amino-1-undecene SAM on the surface. The appearance of the pi-pi* C 1s shakeup peak confirmed the presence of C60 on the surface. Infrared spectroscopic studies verified several characteristic features of the C60 skeleton vibration and the 11-amino-1-undecene vibrational signature. The atomic force microscopy investigation suggested that the fullerene molecules produce surface features with an apparent height of approximately 2 nm and an average width of approximately 20 nm. A parallel study was performed on a Au(111) surface for comparison with the results obtained on the silicon substrate. The reaction between fullerene molecules and approximately 1% 11-amino-1-undecene diluted in decene SAM on the Si(111) surface accordingly yielded dilute and uniformly distributed C60 molecules on the surface, which indicated that the amine groups were the reactive sites.  相似文献   

18.
A novel ferroceneylazobenzene self-assembled monolayer (SAM) has been constructed on an indium-tin oxide (ITO) electrode via the covalent attachment of 4-(4'-11-ferrocenyl-undecanoxyphenylazo)benzoic acid ( FcAzCOOH) onto a silanized ITO substrate surface and verified by reflectance infrared spectroscopy and water contact angle. Atomic force microscopy (AFM) and cyclic voltammogram (CV) indicated that the FcAzCOOH formed a uniform and reproducible SAM on the ITO electrode with a surface coverage of ca. 1.9 x 10 (-10) mol/cm (2) (87 A (2)/molecule). The reversible photoisomerization behavior of the SAM was characterized by UV-vis spectra. The azo pi-pi* transition band intensity of the SAM gradually decreased with UV (365 nm) irradiation and was almost recovered again when subsequent exposure to ambient room light (400-800 nm). The increased tilt angle of the molecules on the ITO substrate after UV irradiation further confirmed the trans-to- cis isomerization of azobenzene moieties. The CV of the trans- FcAzCOOH modified ITO electrode showed a pair of waves due to redox of the ferrocene groups in the potential range of 0 to +800 mV (vs SCE), and the peak separation of the redox wave became larger after UV irradiation and almost returned to its original value after subsequent exposure to the visible light. Rate-dependent CV curves indicated that the charge transfer rate between the ferrocene species in the SAM and the ITO electrode was slowed down after UV irradiation due to the smaller porosity of the monolayer film and the more compact barrier layer between the redox species and the ITO electrode. It is the first time to directly observe the influence of photoisomerization of the azobenzene moiety on the redox behavior of redox species in the ferroceneylazobenzene-functionalized SAM. The present results provide profound insight into the role of redox microenvironment on electron transfer kinetics and also provide a simple and facile approach to the preparation of photocontrollable electrodes.  相似文献   

19.
DNA在氨基功能化偶氮苯自组装膜表面的固定   总被引:1,自引:0,他引:1  
采用简单快速的方法制备出将DNA固定在其表面的单分子层敏感膜.首先采用表面自组装技术将硅氧烷基偶氮苯衍生物H2NAzoCONHC3Si(OCH3)3(APDA-N-TMSPBA)组装在硅表面,在详细考察单分子层薄膜的化学结构、表面浸润性和分子表面形貌之后,又通过紫外吸收光谱(UV)在位考察了硅氧烷基偶氮苯衍生物的光学异构特性.在DNA在自组装薄膜固定后,X光电子能谱仪(XPS)结果显示出现了明显的磷元素信号,表明DNA分子可以成功固定在自组装膜表面.  相似文献   

20.
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