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Enantiospecific electrodeposition of a chiral catalyst

Nature volume 425, pages 490–493 (2003)Cite this article

Abstract

Many biomolecules are chiral—they can exist in one of two enantiomeric forms that only differ in that their structures are mirror images of each other. Because only one enantiomer tends to be physiologically active while the other is inactive or even toxic, drug compounds are increasingly produced in an enantiomerically pure form1 using solution-phase homogeneous catalysts and enzymes. Chiral surfaces offer the possibility of developing heterogeneous enantioselective catalysts that can more readily be separated from the products and reused. In addition, such surfaces might serve as electrochemical sensors for chiral molecules. To date, chiral surfaces have been obtained by adsorbing chiral molecules2,3,4,5,6 or slicing single crystals so that they exhibit high-index faces7,8,9,10,11,12,13, and some of these surfaces act as enantioselective heterogeneous catalysts5,6,10. Here we show that chiral surfaces can also be produced through electrodeposition, a relatively simple solution-based process that resembles biomineralization14,15,16,17 in that organic molecules adsorbed on surfaces have profound effects on the morphology of the inorganic deposits18,19,20. When electrodepositing a copper oxide film on an achiral gold surface in the presence of tartrate ion in the deposition solution, the chirality of the ion determines the chirality of the deposited film, which in turn determines the film's enantiospecificity during subsequent electrochemical oxidation reactions.

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Figure 1: X-ray diffraction of electrodeposited CuO.
Figure 2: Determination of the absolute configuration of chiral CuO. X-ray pole figures of CuO films on Au(001) deposited from a, Cu(ii)(S,S-tartrate), b, Cu(ii)(R,R-tartrate), and c, racemic Cu(ii)(tartrate).
Figure 3: Outline of the enantiospecific electrodeposition scheme.
Figure 4: Chiral recognition by electrodeposited CuO.

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References

  1. Stinson, S. C. Chiral pharmaceuticals. Chem. Eng. News 79, 79–97 (2001)

    Article  Google Scholar 

  2. Lorenzo, M. O., Baddeley, C. J., Muryn, C. & Raval, R. Extended surface chirality from supramolecular assemblies of adsorbed chiral molecules. Nature 404, 376–379 (2000)

    Article  ADS  CAS  Google Scholar 

  3. Humblot, V., Haq, S., Muryn, C., Hofer, W. A. & Raval, R. From local adsorption stresses to chiral surfaces: (R,R)-tartaric acid on Ni(110). J. Am. Chem. Soc. 124, 503–510 (2002)

    Article  CAS  Google Scholar 

  4. Kühnle, A., Linderoth, T. R., Hammer, B. & Besenbacher, F. Chiral recognition in dimerization of adsorbed cysteine observed by scanning tunnelling microscopy. Nature 415, 891–893 (2002)

    Article  ADS  Google Scholar 

  5. Izumi, Y. in Advances in Catalysis Vol. 32, 215–271 (Academic, New York, 1983)

    Google Scholar 

  6. LeBlond, C., Wang, J., Liu, J., Andrews, A. T. & Sun, Y.-K. Highly enantioselective heterogeneously catalyzed hydrogenation of α-ketoesters under mild conditions. J. Am. Chem. Soc. 121, 4920–4921 (1999)

    Article  CAS  Google Scholar 

  7. McFadden, C. F., Cremer, P. S. & Gellman, A. J. Adsorption of chiral alcohols on “chiral” metal surfaces. Langmuir 12, 2483–2487 (1996)

    Article  CAS  Google Scholar 

  8. Horvath, J. D. & Gellman, A. J. Enantiospecific desorption of R- and S-propylene oxide from a chiral Cu(643) surface. J. Am. Chem. Soc. 123, 7953–7954 (2001)

    Article  CAS  Google Scholar 

  9. Horvath, J. D. & Gellman, A. J. Enantiospecific desorption of chiral compounds from chiral Cu(643) and achiral Cu(111) surfaces. J. Am. Chem. Soc. 124, 2384–2392 (2002)

    Article  CAS  Google Scholar 

  10. Ahmadi, A., Attard, G., Feliu, J. & Rodes, A. Surface reactivity at “chiral” platinum surfaces. Langmuir 15, 2420–2424 (1999)

    Article  CAS  Google Scholar 

  11. Attard, G. A. et al. Temperature effects in the enantiomeric electro-oxidation of D- and L-glucose on Pt{643}S. J. Phys. Chem. B 103, 1381–1385 (1999)

    Article  CAS  Google Scholar 

  12. Attard, G. A. Electrochemical studies of enantioselectivity of chiral metal surfaces. J. Phys. Chem. B 105, 3158–3167 (2001)

    Article  CAS  Google Scholar 

  13. Sholl, D. S., Asthagiri, A. & Power, T. D. Naturally chiral metal surfaces as enantiospecific adsorbents. J. Phys. Chem. B 105, 4771–4782 (2001)

    Article  CAS  Google Scholar 

  14. Orme, C. A. et al. Formation of chiral morphologies through selective binding of amino acids to calcite surface steps. Nature 411, 775–779 (2001)

    Article  ADS  CAS  Google Scholar 

  15. Addadi, L. & Weiner, S. Crystals, asymmetry and life. Nature 411, 753–755 (2001)

    Article  ADS  CAS  Google Scholar 

  16. Teng, H. H., Dove, P. M., Orme, C. A. & De Yoreo, J. J. Thermodynamics of calcite growth: baseline for understanding biomineral formation. Science 282, 724–727 (1998)

    Article  ADS  CAS  Google Scholar 

  17. Cody, A. M. & Cody, R. D. Chiral habit modifications of gypsum from epitaxial-like adsorption of stereospecific growth inhibitors. J. Cryst. Growth 113, 508–519 (1991)

    Article  ADS  CAS  Google Scholar 

  18. Paunovic, M. & Schlesinger, M. Fundamentals of Electrochemical Deposition 167–186 (Wiley-Interscience, New York, 1998)

    Google Scholar 

  19. Josell, D., Wheeler, D., Huber, W. H. & Moffat, T. P. Superconformal electrodeposition in submicron features. Phys. Rev. Lett. 87, 016102 (2001)

    Article  ADS  CAS  Google Scholar 

  20. Vazhev, V. V. & Mardashev, Yu. S. A “memory” effect in formic and oxalic acid oxidation at gold electrodes. Sov. Electrochem. 16, 1445–1447 (1980)

    Google Scholar 

  21. Switzer, J. A., Shumsky, M. G. & Bohannan, E. W. Electrodeposited ceramic single crystals. Science 284, 293–296 (1999)

    Article  ADS  CAS  Google Scholar 

  22. Bohannan, E. W., Shumsky, M. G. & Switzer, J. A. Epitaxial electrodeposition of copper(I) oxide on single-crystal Au(100). Chem. Mater. 11, 2289–2291 (1999)

    Article  CAS  Google Scholar 

  23. Sorenson, T. A., Morton, S. A., Waddill, G. D. & Switzer, J. A. Epitaxial electrodeposition of Fe3O4 thin films on the low-index planes of gold. J. Am. Chem. Soc. 124, 7604–7609 (2002)

    Article  CAS  Google Scholar 

  24. Switzer, J. A., Kothari, H. M. & Bohannan, E. W. Thermodynamic to kinetic transition in epitaxial electrodeposition. J. Phys. Chem. B 106, 4027–4031 (2002)

    Article  CAS  Google Scholar 

  25. Switzer, J. A., Liu, R., Bohannan, E. W. & Ernst, F. Epitaxial electrodeposition of a crystalline metal oxide onto single-crystalline silicon. J. Phys. Chem. B 106, 12369–12372 (2002)

    Article  CAS  Google Scholar 

  26. Poizot, P., Hung, C.-J., Nikiforov, M. P., Bohannan, E. W. & Switzer, J. A. An electrochemical method for CuO thin film deposition from aqueous solution. Electrochem. Solid-State Lett. 6, C21–C25 (2003)

    Article  CAS  Google Scholar 

  27. Catana, A., Locquet, J.-P., Paik, S. M. & Schuller, I. K. Local epitaxial growth of copper monoxide films on magnesium oxide. Phys. Rev. B 46, 15477–15483 (1992)

    Article  ADS  CAS  Google Scholar 

  28. Missavage, R. J., Belford, R. L. & Paul, I. C. Crystal and molecular structure of tetrasodium dicopper(ii)-dl-tartrate decahydrate. J. Coord. Chem. 2, 145–157 (1972)

    Article  CAS  Google Scholar 

  29. Hazen, R. M., Filley, T. R. & Goodfriend, G. A. Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality. Proc. Natl Acad. Sci. USA 98, 5487–5490 (2001)

    Article  ADS  CAS  Google Scholar 

  30. Xie, Y. & Huber, C. O. Electrocatalysis and amperometric detection using an electrode made of copper oxide and carbon paste. Anal. Chem. 63, 1714–1719 (1991)

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Science Foundation and the University of Missouri Research Board.

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  1. Department of Chemistry and Graduate Center for Materials Research, University of Missouri-Rolla, Rolla, Missouri, 65409-1170, USA

    Jay A. Switzer, Hiten M. Kothari, Philippe Poizot, Shuji Nakanishi & Eric W. Bohannan

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Correspondence to Jay A. Switzer.

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Switzer, J., Kothari, H., Poizot, P. et al. Enantiospecific electrodeposition of a chiral catalyst. Nature 425, 490–493 (2003). https://doi.org/10.1038/nature01990

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