| 1. |
- Liedberg, Bo, et al.
(författare)
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Self-assembly of alpha-functionalized terthiophenes on gold
- 1997
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Ingår i: JOURNAL OF PHYSICAL CHEMISTRY B. - : AMER CHEMICAL SOC. - 1089-5647 .- 1520-6106 .- 1520-5207. ; 101:31, s. 5951-5962
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Tidskriftsartikel (refereegranskat)abstract
- alpha-Functionalized terthiophenes containing disulfide (-S-T-3-H)(2) and alkanethiol (HS-(CH2)(11)-T-3-H) anchoring groups have been synthesized for direct immobilization onto gold. Monolayer structures of these compounds are prepared by spontaneous assembly from ethanol solutions on evaporated gold substrates and thoroughly characterized by ellipsometry, contact angle goniometry, infrared and X-ray photoelectron spectroscopy, and cyclic voltammetry. The two molecules coordinate to the gold substrate exclusively via the anchoring groups upon formation of gold-thiolate bonds. The kinetics of monolayer formation vary dramatically for the two compounds. The alkanethiol analogue assembles rapidly, within a few minutes, and forms a densely packed and highly organized monolayer, with the alkyl chains in an almost perfect all-trans conformation and the C-alpha-C-alpha axis of the alpha-T-3 units tilted about 14 degrees away from the surface normal. The assembly process is much slower for the disulfide, but an organized monolayer with an average alpha-T-3 chain tilt of about 33 degrees will eventually form when the assembly is allowed to equilibrate with a solution containing the disulfide for at least 1 day. Moreover, the two monolayer assemblies also display a remarkably different electrochemical, behavior. The heterogeneous electron-transfer rate at the disulfide-covered gold substrate is almost indistinguishable from that at bare gold, suggesting that the assembly contains a large number of easily accessible defects. An alternative mechanism for explaining the large electron-transfer rate involving electronic coupling via the conjugated pi-system of the alpha-T-3 units is also proposed. The electrochemical response is significantly reduced for the HS-(CH2)(11)-T-3-H assembly, but another type of defects, the so-called shallow defects originating from sparsely populated areas on the electrode surface, can be identified.
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| 2. |
- Yang, Zhongping, et al.
(författare)
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Preparation and characterization of mixed monolayer assemblies composed of thiol analogues of cholesterol and fatty acid
- 1997
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Ingår i: Langmuir. - : American Chemical Society. - 0743-7463 .- 1520-5827. ; 13:12, s. 3210-3218
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Tidskriftsartikel (refereegranskat)abstract
- Mixed self-assembled monolayers provide an attractive model system for investigating the role of different molecules in biological membranes. This paper describes the preparation and characterization of a novel type of mixed monolayer assemblies composed of thiol analogues of cholesterol and fatty acid. The mixed: monolayers are prepared by coadsorbing 11-mercaptoundecanoic acid (MUA) and thiocholesterol(cholest-5-ene-3 beta-thiol, TC) from solution directly onto evaporated gold surfaces. The influence of TC on the molecular composition and conformation in the mixed monolayer is analyzed by using a combination of infrared reflection-absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS), ellipsometry, contact angle measurement, and cyclic voltammetry. The results indicate that the TC molecules maintain their conformation in the mixed monolayers, whereas the MUA molecules display a significantly more disordered conformation as compared to the MUA molecules in the pure monolayer. Cyclic voltammetry shows that the mixed monolayers are more densely packed and less permeable than the pure TC and MUA monolayers. The kinetics of the coadsorption of TC and MUA from ethanol indicates that adsorption of TC initially is strongly preferred over MUA but that MUA dominates over TC at long coadsorption times. This is because there is a larger energy gain per unit area in forming monolayers with MUA, Further, it is also seen that the number of molecules per unit area changes with the molecular composition, as a consequence of the different sizes of TC and MUA. We present herein a method for calculating the mole fraction of TC on the gold surface, (chi TC), which accounts for this variation. As a consequence of the dissimilar size and shape of the two molecules, the wetting properties of the mixed monolayer are found to be mainly governed by the fractional area of TC, rather than by the molecular composition of TC, (chi TC).
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| 3. |
- Lestelius, Magnus, et al.
(författare)
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Order/disorder gradients of n-alkanethiols on gold
- 1999
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Ingår i: Colloids and Surfaces B. - : Elsevier. - 0927-7765 .- 1873-4367. ; 15:1, s. 57-70
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Tidskriftsartikel (refereegranskat)abstract
- This paper explores the interfacial properties of one-dimensional molecular gradients of alkanethiols (HS-(CH2)(n)- X) on gold. The kinetics and thermodynamics of monolayer formation are important issues for these types of mixed molecular assemblies. The influence of chain length difference on the contact angles with hexadecane (HD), theta(a) and theta(r), and the hysteresis, has been studied by employing alkanethiols HS-(CH2)(n)-CH3, with n = 9, 11, 13, 15 and 17, in the preparation of the self-assembled monolayers (SAM) gradients. The contact angles with hexadecane, at the very extreme ends of the gradients, show characteristic values of a highly ordered CH3-like assembly: theta(a) = 45-50 degrees. In the middle of the gradients theta(a) drops noticeably and exhibits values representative for CH2-like polymethylenes, theta(a) = 20-30 degrees, indicating a substantial disordering of the protruding chains of the longer component in the gradient assembly. As expected, the exposure of CH2-groups to the probing liquid increases with increasing differential chain length of the two n-alkanethiol used, in this case eight methylene units. However, the contact angles always display a non-zero value which means that even at a chain length difference of eight methylene units there is a substantial exposure of methyl (CH3) groups to the probing liquid. With infrared reflection-absorption spectroscopy (IRAS) we have monitored the structural behavior of the polymethylene chains along the gradient. We find complementary evidence for disordered chains in the gradient region, and the IRAS results correlate well with the contact angle measurements. (C) 1999 Elsevier Science B.V. All rights reserved.
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| 4. |
- Yang, Z. P., et al.
(författare)
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Thiocholesterol on gold : A nanoporous molecular assembly
- 1996
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Ingår i: Langmuir. - : American Chemical Society. - 0743-7463 .- 1520-5827. ; 12:7, s. 1704-1707
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Tidskriftsartikel (refereegranskat)abstract
- The formation of thiocholesterol (TC) monolayers on gold has been studied by ellipsometry, contact angle measurements, infrared spectroscopy, and cyclic voltammetry. Subsequent treatment of the TC assembly with 11-mercaptodeuterioundecanoic acid (MDUA) shows that the average surface coverage is about 65% of that of a self-assembled alkanethiolate monolayer and that it has a large number of molecular defects. These defects exist because of a mismatch between the size and shape of the TC molecule and the pinning distance at the Au(111) crystal lattice. Potential uses of these defect-rich structures are microelectrode arrays for electroanalytical and biosensor applications.
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