Chiral electrode surfaces

In 1975, the fabrication of a chiral electrode by permanent attachment of amino acid residues to pendant groups on a graphite surface was reported At the same time, stimulated by the development of bonded phases on silica and aluminia surfaces the first example of derivatized metal surfaces for use as chemically modified electrodes was presented. A silanization technique was used for covalently binding redox species to hydroxy groups of SnOj or Pt surfaces. Before that time, some successful attemps to create electrode surfaces with deliberate chemical properties made use of specific adsorption techniques... 

A qualitatively new approach to the surface pretreatment of solid electrodes is their chemical modification, which means a controlled attachment of suitable redox-active molecules to the electrode surface. The anchored surface molecules act as charge mediators between the elctrode and a substance in the electrolyte. A great effort in this respect was triggered in 1975 when Miller et al. attached the optically active methylester of phenylalanine by covalent bonding to a carbon electrode via the surface oxygen functionalities (cf. Fig. 5.27). Thus prepared, so-called chiral electrode showed stereospecific reduction of 4-acetylpyridine and ethylph-enylglyoxylate (but the product actually contained only a slight excess of one enantiomer). 

Attempts to achieve optical induction during the reduction of aromatic ketones to the secondary alcohol by immobilising a single layer of chiral catalyst on a solid electrode surface have been much less successful. The preparation of such coatings... 

Using a different dimerization method, namely phenolic oxidation, chiral substrates react in a more stereoselective manner than under reductive conditions. The choice of oxidizing reagent may drastically affect the stereochemical outcome of the reaction. Thus, when potassium hexacyanoferrate(III) is used (17 )-l,2,3,4-tetrahydro-6-methoxy-l,2-dimethyl-7-isoquino-linol couples to give a mixture of atropisomers 3 in 38 % yield and with a d.r. (M)I(P) of 45 553,4. Only one single atropisomer, namely (A/)-3, is formed, in a 66% yield by anodic oxidation, which is attributed to electrode surface effects3. 

The electrode surfaces of a normal LCD sandwich cell d 8-10 pm) are coated with an alignment layer in order to induce a planar alignment of a host (chiral) nematic mixture containing the dichroic dye of positive dichroism and a chiral dopant. Due to the absence of polarisers a very thin mirror can be incorporated within the cell on top of the rear glass plate electrode in direct contact with the guest-host mixture, see Figure 3.15. 

The asymmetric eiectroreduction of an imino group has also been the subject of several studies. The use of modified electrodes,or chiral additives that supposedly create a chiral environment close to the electrode surface, give only low optical yields. 49,so other strategies will have to be explored in order to obtain high optical purities useful for synthetic work. 

The influence of a surface on an adsorbed species is well-accepted. The TA/Ni(l 10) system demonstrates how much the molecule can influence the behaviour of the surface. How far can an adsorbate like tartaric acid induce such effects Work by Switzer and co-workers on the electrodeposition of CuO films in the presence of tartaric acid showed that chirality could be induced in a normally achiral inorganic material [25]. In a standard electrochemical cell, a Au(OOl) crystal is placed in a solution containing Cu(II) ions, tartrate ions and NaOH. At a certain potential, CuO will deposit, as a thin-film on the Au Surface. Characterization by diffraction revealed that the deposited CuO film has no mirror or inversion elements, i.e. it is chiral. The chirality of the film is controlled by the chirality of the tartrate ions in the solution (/ ,/ )-tartrate yielding a chiral CuO(-lll) fihn while presence of (S,S )-tartrate produces the mirror Cu(l-l-l) enantiomorph. Switzer et al, by catalyzing the oxidation of tartaric acid, demonstrate that not only the bulk, but also the surface of the CuO film is chiral the CuO electrode surface grown in the presence of (/ ,/ )-tartrate is more effective at oxidizing (/ ,/ )-TA, while the surface deposited in the presence of (S,S )-tartrate is more effective at oxidizing (S,S )-TA. 

Very recently it has been shown that electrode surfaces can be chemically modified.13 Although no useful reactions have come from this work, it has been shown that organic molecules can be covalently attached to electrode surfaces and that these modified surfaces impart selectivity to electrochemical reactions which is not otherwise available. Attempts have also been made to increase the selectivity of electrochemical reactions by adsorbing material on the electrode surface. In particular if chiral alkaloids are adsorbed on mercury, it Is then possible to perform the asymmetric reduction of prochiral ketones tc chiral alcohols. An optical yield of 54% has, for example, been reported for the reduction of 4-acetyl pyridine in aqueous-ethanol using strychnine as the catalytic, chiral reagent.11 ... 

The low enantioselectivity in these cases can be explained by low coverage of chiral species on electrode surfaces. Therefore, some attempts were undertaken to use metal hydrogenating catalysts as electrode materials. But at first only ee values of 2-6% were obtained in the reduction of 2-oxo compounds into alcohols using Raney-Ni powder electrodes modified with... 

C-H oxidation (150). The Jacobsen s ligand has been used for the modification of the manganese exchanged Al-MCM-41, that is the immobilized catalyst has been investigated in epoxidation of styrene (151). Chiral manganese-Schiff base complexes were immobilized on a glassy carbon electrode surface (152). Enan-tioselective epoxidation reactions were also catalyzed with Mn(III) complexes of chiral porphirines (97,153). 

The concept of enantioselective electrical contacting of redox enzymes and electrode surfaces was further developed by the organization of a chiral... 

Because of electrode surface area enhancement and their high aspect ratio, CNTs support the production of high current density when used to construct enzyme cathodes and anodes. CNTs are constructed as multiwalled (MWCNT) or single-walled (SWCNT) configurations with various chiral vectors. Engineering the bio-nano interface involves careful selection and application of CNTs with specific properties that enhance DET between the conductive carbon architecture and the biocatalyst. Electrodes composed of (or decorated with) CNTs have a larger surface area for enzyme immobihzation than conventional carbon surfaces the enlarged electrode surface area increases the current density. 

Provided electron transfer between the electrode and solute species is not interrupted by the coating, even electroinactive films can offer interesting applications. Thus, a chiral environment in the surface layer may impose stereoselectivity in the follow-up reactions of organic or organometallic intermediates. Furthermore, polymer layers may be used to obtain diffusional permeation selectivity for certain substrates, or as a preconcentration medium for analyzing low concentration species. 

From this discussion it is clear, that, independently of their redox properties, suitably modified electrodes offer themselves for the introduction of diastereo- or enantioselectivity into electrochemistry. Early reports of chiral inductions at modified electrodes include reactions at graphite and SnO surfaces derivatized with monolayers of (S)-(—)-phenylalanine. Asymmetric inductions at the chiral graphite electrode could, however, not be verified in other laboratories even after great efforts... 

Alkyl aryl sulfides were anodically oxidized to the corresponding chiral sulfoxides by using poly(amino acid[-coated electrodes. Partially very high enantioselec-tivities (93% ee) were reported [374, 375] however, the reproducibility depended strongly on the lot of the poly(amino acid) used [376]. Earlier, with a similar approach, by using an edge surface graphite anode that was chemically modified with (.S )-phenylalanine, an enantioselectivity of 0.5 to 2.5% was found in the oxidation of methylp-tolyl sulfide to the sulfoxide [377]. 

The HOPG (highly oriented pyrolytic graphite) carbon electrode chemically modified with (5[-phenylalanine at the basal surface led to 2% ee in the reduction of 4-acetylpyridine [377]. A cathode modified with a chiral poly(pyrrole) reduced 4-methylbenzophenone or acetophenone in DMF/LiBr and phenol as proton donor to 1-phenylethanol with up to 17% ee [382]. Alkyl aryl ketones have been reduced to the corresponding alcohols at a Hg cathode in DMF/water in the presence of (1R,2S)-A,A-dimethylephedrinium tetrafluorobo-rate (DET), producing (5 )-l-phenylethanol with 55% ee from acetophenone. Cyclovoltammetry supports an enantioselective protonation of the intermediate (PhCOH(CH3)) [383]. 

Without doubt, the advent of carbon nanotubes has opened up iimovative perspectives for research and development of carbon electrodes. In this chapter, we have attempted to highlight the electrochemical properties of carbon nanotubes by rooting them mainly on their structural, electronic and chemical properties. If chirality of SWNTs could be controlled, it would be possible to probe electrochemically the unique electronic properties of the tubes with their corresponding unique DOS distribution and establish direct correlations between electronic structure and electrochemistry. However, so far, most of their electrochemical applications are based on ensembles of CNTs (MWNTs or SWNTs) in thin films supported on conductive surfaces or composites. Such ensembles, not so well defined from the structural point of view, contain a mixture of tubes with different diameters and DOS... 

MIP films, applied to a QCM transducer, have been employed for chiral recognition of the R- and 5-propranolol enantiomers [107]. MIP films were prepared for that purpose by surface grafted photo-radical polymerization. First, a monolayer of 11-mercaptoundecanoic acid was self-assembled on a gold electrode of the quartz resonator. Then, a 2,2 -azobis(2-amidinopropane) hydrochloride initiator (AAPH), was attached to this monolayer. Subsequently, this surface-modified resonator was immersed in an ACN solution containing the MAA functional monomer, enantiomer template and trimethylolpropane trimethacrylate (TRIM) cross-linker. Next, the solution was irradiated with UV light for photopolymerization. The resulting MIP-coated resonator was used for enantioselective determination of the propranolol enantiomers under the batch [107] conditions and the FIA [107] conditions with an aqueous-ACN mixed solvent solution as the carrier. The MIP-QCM chemosensor was enantioselective to 5-propranolol at concentrations exceeding 0.38 mM [107]. 

Maltodextrins (dextrose equivalent (DE) 4.0-7.0, 13.0-17.0 and 16.5-19.5) are proposed as novel chiral selectors for the construction of EPMEs for S-captopril assay [36]. The EPMEs can be used reliably for the assay of S-captopril as raw material and from pharmaceutical formulations as Novocaptopril tablets, using direct potentiometry. The best response was obtained when maltodextrin with higher DE was used for the electrode s construction. The best enantioselectivity and stability in time was achieved for the lower DE maltodextrin. L-Proline was found to be the main interferent for all proposed electrodes. The surface of the electrodes can be regenerated by simply polishing, obtaining a fresh surface ready to be used in a new assay. 

A particular class of modified electrodes consists of those containing a layer of asymmetric compounds, and such electrodes are termed chiral. If one uses these electrodes in organic synthesis, the compound produced may also be asymmetric and optically active. One of the better-known examples of such phenomena is called the Sharpless process (Finn and Sharpless, 1986 Katsuki, 1996). In such processes, the electrode is modified by asymmetric compounds that lead to epoxidation and dihy-droxylation of olefenic compounds, but in an asymmetric form. An example is shown in Fig. 11.5, in which the hydroxylation occurs either on the top or the bottom of the enantiomorphic surface. 

Recently, considerable interest has been shown for electrodes on which the surface has been modified chemically (CME, chemically modified electrodes). The emphasis in the investigations has mainly been on studying the preparation, properties, and mechanism of the electron transfer, but gradually the emphasis in the field is shifting to applications the use of CME for induction of chirality is treated in Chapter 26. 

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