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Kinetic dispersion in redox-active dithiocarbamate monolayers.

ABSTRACT: Dithiocarbamates (dtcs) have been implicated as important gold-binding groups in molecular electronics. Dtcs have two alkane branches connected at a single anchoring point that has a bidentate resonance structure. Forming readily in situ by the combination of secondary amines and CS(2), dtcs adsorb quickly onto gold surfaces. Electroactive self-assembled monolayers (eSAMs) were prepared by the coadsorption of ferrocene dialkyldithiocarbamates (Fc dtcs) with diluent dtcs on gold electrodes. Short and long alkane chains were used (11 and 16 methylene groups, respectively), and a polar ester group was incorporated. Cyclic voltammetry (CV) shows that the electrochemistry is quasi-reversible. At high surface coverage, the peak separations and full widths at half-maximum for Fc dtcs deviate from theoretical values and are analogous to that of ferrocene alkane thiols on gold at high surface coverage. Importantly, these features do not change at low Fc dtc surface coverage as observed for ferrocene alkane thiols. Ferrocene dtcs were used to label monolayer defect sites and to demonstrate the exchange of surface-bound dtcs with solution dtcs. Finally, the rate of electron transfer was analyzed using Tafel plots and ac voltammetric methods. The results for both techniques are consistent with a kinetically disperse population of redox sites. The length of the diluent alkane chain appears to have an effect on the distribution of electron-transfer rates, likely because of the eSAM structure. This work indicates that structurally, Fc dtc eSAMs are fundamentally different from alkane thiol SAMs on gold.

SUBMITTER: Eckermann AL

PROVIDER: S-EPMC4477844 | biostudies-literature | 2010 Feb

REPOSITORIES: biostudies-literature

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Kinetic dispersion in redox-active dithiocarbamate monolayers.

Eckermann Amanda L AL Shaw Justine A JA Meade Thomas J TJ

Langmuir : the ACS journal of surfaces and colloids 20100201 4

Dithiocarbamates (dtcs) have been implicated as important gold-binding groups in molecular electronics. Dtcs have two alkane branches connected at a single anchoring point that has a bidentate resonance structure. Forming readily in situ by the combination of secondary amines and CS(2), dtcs adsorb quickly onto gold surfaces. Electroactive self-assembled monolayers (eSAMs) were prepared by the coadsorption of ferrocene dialkyldithiocarbamates (Fc dtcs) with diluent dtcs on gold electrodes. Short ...[more]

PMID: 19877702

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Project description:The background: The monolayers self-assembled on the gold electrode incorporated transition metal complexes can act both as receptor ("host" molecules) immobilization sites, as well as transducer for interface recognitions of "guest" molecules present in the aqueous solutions. Their electrochemical parameters influencing the sensing properties strongly depend on the transition metal complex structures. The objectives: The electrochemical characterization of the symmetric terpyridine-M2+-terpyridine and asymmetric dipyrromethene-M2+-terpyridine complexes modified with ssDNA probe covalently attached to the gold electrodes and exploring their ssDNA sensing ability were the main aims of the research presented. The methods: Two transition metal cations have been selected: Cu2+ and Co2+ for creation of redox-active monolayers. The electron transfer coefficients indicating the reversibility and electron transfer rate constant measuring kinetic of redox reactions have been determined for all SAMs studied using: Cyclic Voltammetry, Osteryoung Square-Wave Voltammetry, and Differential Pulse Voltammetry. All redox-active platforms have been applied for immobilization of ssDNA probe. Next, their sensing properties towards complementary DNA target have been explored electrochemically. The results: All SAMs studied were stable displaying quasi-reversible redox activity. The linear relationships between cathodic and anodic current vs. san rate were obtained for both symmetric and asymmetric SAMs incorporating Co2+ and Cu2+, indicating that oxidized and reduced redox sites are adsorbed on the electrode surface. The ssDNA sensing ability were observed in the fM concentration range. The low responses towards non-complementary ssDNA sequences provided evidences for sensors good selectivity. The conclusions: All redox-active SAMs modified with a ssDNA probe were suitable for sensing of ssDNA target, with very good sensitivity in fM range and very good selectivity. The detection limits obtained for SAMs incorporating Cu2+, both symmetric and asymmetric, were better in comparison to SAMs incorporating Co2+. Thus, selection of the right transition metal cation has stronger influence on ssDNA sensing ability, than complex structures.

Project description:BACKGROUND: The interest in introducing ecologically-clean, and efficient enzymes into modern industry has been growing steadily. However, difficulties associated with controlling their orientation, and maintaining their selectivity and reactivity is still a significant obstacle. We have developed precise immobilization of biomolecules, while retaining their native functionality, and report a new, fast, easy, and reliable procedure of protein immobilization, with the use of Adenylate kinase as a model system. METHODS: Self-assembled monolayers of hexane-1,6-dithiol were formed on gold surfaces. The monolayers were characterized by contact-angle measurements, Elman-reagent reaction, QCM, and XPS. A specifically designed, mutated Adenylate kinase, where cysteine was inserted at the 75 residue, and the cysteine at residue 77 was replaced by serine, was used for attachment to the SAM surface via spontaneously formed disulfide (S-S) bonds. QCM, and XPS were used for characterization of the immobilized protein layer. Curve fitting in XPS measurements used a Gaussian-Lorentzian function. RESULTS AND DISCUSSION: Water contact angle (65-70°), as well as all characterization techniques used, confirmed the formation of self-assembled monolayer with surface SH groups. X-ray photoelectron spectroscopy showed clearly the two types of sulfur atom, one attached to the gold (triolate) and the other (SH/S-S) at the ?-position for the hexane-1,6-dithiol SAMs. The formation of a protein monolayer was confirmed using XPS, and QCM, where the QCM-determined amount of protein on the surface was in agreement with a model that considered the surface area of a single protein molecule. Enzymatic activity tests of the immobilized protein confirmed that there is no change in enzymatic functionality, and reveal activity ~100 times that expected for the same amount of protein in solution. CONCLUSIONS: To the best of our knowledge, immobilization of a protein by the method presented here, with the resulting high enzymatic activity, has never been reported. There are many potential applications for selective localization of active proteins at patterned surfaces, for example, bioMEMS (MEMS--Micro-Electro-Mechanical Systems. Due to the success of the method, presented here, it was decided to continue a research project of a biosensor by transferring it to a high aspect ratio platform--nanotubes.

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Kinetic dispersion in redox-active dithiocarbamate monolayers.

Publications

Kinetic dispersion in redox-active dithiocarbamate monolayers.

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