Boronic acid-protected gold clusters capable of asymmetric induction: spectral deconvolution analysis of their electronic absorption and magnetic circular dichroism.

Gold clusters protected by 3-mercaptophenylboronic acid (3-MPB) with a mean core diameter of 1.1 nm are successfully isolated, and their absorption, magnetic circular dichroism (MCD), and chiroptical responses in metal-based electronic transition regions, which can be induced by surface D-/L-fructose complexation, are examined. It is well-known that MCD basically corresponds to electronic transitions in the absorption spectrum, so simultaneous deconvolution analysis of electronic absorption and MCD spectra of the gold cluster compound is conducted under the constrained requirement that a single set of Gaussian components be used for their fitting. We then find that fructose-induced chiroptical response is explained in terms of the deconvoluted spectra experimentally obtained. We believe this spectral analysis is expected to benefit better understanding of the electronic states and the origin of the optical activity in chiral metal clusters.

[1]  R. Jin,et al.  Isolation of ubiquitous Au(40)(SR)(24) clusters from the 8 kDa gold clusters. , 2010, Journal of the American Chemical Society.

[2]  S. Franzen,et al.  Infrared detection of a phenylboronic acid terminated alkane thiol monolayer on gold surfaces. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[3]  Younan Xia,et al.  Shape-controlled synthesis of metal nanostructures: the case of silver. , 2005, Chemistry.

[4]  A. Baiker Progress in asymmetric heterogeneous catalysis: Design of novel chirally modified platinum metal catalysts , 1997 .

[5]  H. Snyder,et al.  Aryl Boronic Acids. II. Aryl Boronic Anhydrides and their Amine Complexes1 , 1958 .

[6]  J. Lakowicz,et al.  Spectral Properties of Fluorophores Combining the Boronic Acid Group with Electron Donor or Withdrawing Groups. Implication in the Development of Fluorescence Probes for Saccharides. , 2001, The journal of physical chemistry. A.

[7]  T. Goodson,et al.  Quantum-sized gold clusters as efficient two-photon absorbers. , 2008, Journal of the American Chemical Society.

[8]  Thomas Bürgi,et al.  Chiral gold nanoparticles. , 2009, Chemphyschem : a European journal of chemical physics and physical chemistry.

[9]  R. Jin,et al.  Kinetically controlled, high-yield synthesis of Au25 clusters. , 2008, Journal of the American Chemical Society.

[10]  R. Jin,et al.  Reversible switching of magnetism in thiolate-protected Au25 superatoms. , 2009, Journal of the American Chemical Society.

[11]  W. Mason A practical guide to magnetic circular dichroism spectroscopy , 2007 .

[12]  Thomas Bürgi,et al.  Ligand exchange reactions on Au(38) and Au(40) clusters: a combined circular dichroism and mass spectrometry study. , 2010, Journal of the American Chemical Society.

[13]  Hannu Häkkinen,et al.  When Gold Is Not Noble: Nanoscale Gold Catalysts , 1999 .

[14]  Mathias Brust,et al.  Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid system , 1994 .

[15]  H. Kuivila,et al.  ARENEBORONATES FROM DIOLS AND POLYOLS1 , 1954 .

[16]  A. Ceulemans,et al.  Recognition of chiral catechols using oxo-titanium phthalocyanine. , 2004, Journal of the American Chemical Society.

[17]  H. Yao Optically Active Gold Nanoclusters , 2008 .

[18]  R. Jin,et al.  Chiral Au₂₅ nanospheres and nanorods: synthesis and insight into the origin of chirality. , 2011, Nano letters.

[19]  R. Jin,et al.  Facile, large-scale synthesis of dodecanethiol-stabilized Au38 clusters. , 2009, The journal of physical chemistry. A.

[20]  J. C. Norrild,et al.  Boronic acids as fructose sensors. Structure determination of the complexes involved using 1JCC coupling constants , 1996 .

[21]  M. Tinkham,et al.  Coulomb blockade and discrete energy levels in Au nanoparticles , 1998 .

[22]  Y. Negishi,et al.  Ubiquitous 8 and 29 kDa gold:alkanethiolate cluster compounds: mass-spectrometric determination of molecular formulas and structural implications. , 2008, Journal of the American Chemical Society.

[23]  R. Whetten,et al.  A unified view of ligand-protected gold clusters as superatom complexes , 2008, Proceedings of the National Academy of Sciences.

[24]  C. Aikens,et al.  Geometric and Electronic Structure of Au25(SPhX)18− (X = H, F, Cl, Br, CH3, and OCH3) , 2010 .

[25]  H. Gilman,et al.  Some Bromine-containing and Sulfur-containing Aromatic Bornic Acids , 1958 .

[26]  D. Astruc,et al.  Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. , 2004, Chemical reviews.

[27]  H. F. Shurvell,et al.  Infrared spectra of phenylboronic acid (normal and deuterated) and diphenyl phenylboronate , 1968 .

[28]  R. Whetten,et al.  Giant Gold−Glutathione Cluster Compounds: Intense Optical Activity in Metal-Based Transitions , 2000 .

[29]  R. Murray,et al.  Monolayer-protected cluster molecules. , 2000, Accounts of chemical research.

[30]  James E. Hutchison,et al.  Monolayers in Three Dimensions: NMR, SAXS, Thermal, and Electron Hopping Studies of Alkanethiol Stabilized Gold Clusters , 1995 .

[31]  Itamar Willner,et al.  Integrated nanoparticle-biomolecule hybrid systems: synthesis, properties, and applications. , 2004, Angewandte Chemie.

[32]  T. Yokoyama,et al.  X-ray magnetic circular dichroism of size-selected, thiolated gold clusters. , 2006, Journal of the American Chemical Society.

[33]  P. Brown,et al.  Use of Phenylboronic Acids to Investigate Boron Function in Plants. Possible Role of Boron in Transvacuolar Cytoplasmic Strands and Cell-to-Wall Adhesion , 2004, Plant Physiology.

[34]  H. Yao,et al.  Large optical activity of gold nanocluster enantiomers induced by a pair of optically active penicillamines. , 2005, Journal of the American Chemical Society.

[35]  M. Stillman,et al.  Photochemical Formation of the Anion Radical of Zinc Phthalocyanine and Analysis of the Absorption and Magnetic Circular Dichroism Spectral Data. Assignment of the Optical Spectrum of [ZnPc(-3)]- , 1994 .

[36]  O. Lopez-Acevedo,et al.  Chirality and electronic structure of the thiolate-protected Au38 nanocluster. , 2010, Journal of the American Chemical Society.

[37]  C. Noguez,et al.  Optically active metal nanoparticles. , 2009, Chemical Society reviews.

[38]  S. Shinkai,et al.  Chiral discrimination of monosaccharides using a fluorescent molecular sensor , 1995, Nature.

[39]  Y. Negishi,et al.  Extremely high stability of glutathionate-protected Au25 clusters against core etching. , 2007, Small.

[40]  A. M. Alvarez,et al.  Crystal Structures of Molecular Gold Nanocrystal Arrays , 1999 .

[41]  Robert L. Whetten,et al.  Isolation and Selected Properties of a 10.4 kDa Gold:Glutathione Cluster Compound , 1998 .

[42]  P. Stephens Magnetic Circular Dichroism , 1974 .

[43]  Taro Kimura,et al.  Saccharide Induction of Chiral Orientation of the Aggregate Formed from Boronic-Acid-Appended Amphiphiles , 1998 .

[44]  M. Stillman,et al.  Band Deconvolution Analysis of the Absorption and Magnetic Circular Dichroism Spectral Data of ZnPc(-2) Recorded at Cryogenic Temperatures , 1995 .

[45]  K. Kontturi,et al.  Electrochemical resolution of 15 oxidation states for monolayer protected gold nanoparticles. , 2003, Journal of the American Chemical Society.

[46]  R. Shallenberger Intrinsic chemistry of fructose , 1978 .

[47]  R. Naaman,et al.  The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates. , 2006, Physical chemistry chemical physics : PCCP.

[48]  Masatake Haruta,et al.  Size- and support-dependency in the catalysis of gold , 1997 .

[49]  D. C. Roberts,et al.  Chemical affinity systems—I: pH dependence of boronic acid-diol affinity in aqueous solution , 1980 .

[50]  John O. Edwards,et al.  Polyol Complexes and Structure of the Benzeneboronate Ion , 1959 .

[51]  E. Coronado,et al.  The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment , 2003 .

[52]  C. Noguez,et al.  On the origin of the optical activity displayed by chiral-ligand-protected metallic nanoclusters. , 2010, Journal of the American Chemical Society.

[53]  C. D. Geddes,et al.  Complexation of polysaccharide and monosaccharide with thiolate boronic acid capped on silver nanoparticle. , 2004, Analytical biochemistry.

[54]  A. C. Jamison,et al.  4-Mercaptophenylboronic acid SAMs on gold: comparison with SAMs derived from thiophenol, 4-mercaptophenol, and 4-mercaptobenzoic acid. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[55]  William R. Browett,et al.  Computer-aided chemistry - II. A spectral database management program for use with microcomputers , 1987, Comput. Chem..

[56]  R. Whetten,et al.  The colours of nanometric gold , 2007 .

[57]  M. Zaitoun,et al.  Magnetic Circular Dichroism Spectra for Colloidal Gold Nanoparticles in Xerogels at 5.5 K , 2001 .

[58]  R. Naaman,et al.  Molecular chirality and charge transfer through self-assembled scaffold monolayers. , 2006, The journal of physical chemistry. B.

[59]  H. Yao,et al.  Induced Optical Activity in Boronic-Acid-Protected Silver Nanoclusters by Complexation with Chiral Fructose† , 2010 .

[60]  T. Tosa Industrial application of immobilized biocatalysts , 1991 .