Generation of Singlet Oxygen by Photoexcited Au25(SR)18 Clusters

The generation of highly reactive singlet oxygen (1O2) is of major importance for a variety of applications such as photodynamic therapy (PDT) for cancer treatment, water treatment, catalytic oxidation, and others. Herein, we demonstrate that 1O2 can be efficiently produced through the direct photosensitization by Au25(SR)18– clusters (H−SR = phenylethanethiol or captopril) without using conventional organic photosensitizers under visible/near-IR (532, 650, and 808 nm) irradiation. 1O2 was successfully detected by direct observation of the characteristic 1O2 emission around 1276 nm as well as three different 1O2-selective probes. Water-soluble Au25(captopril)18– clusters were explored for cytocompatibility and photodynamic activity toward cancer cells. In addition, selective catalytic oxidation of organic sulfide to sulfoxide by 1O2 was demonstrated on the photoexcited Au25(SC2H4Ph)18– clusters. It is suggested that the optical gap of Au25(SR)18 clusters (∼1.3 eV) being larger than the energy of 1O2 (0.97...

[1]  J. L. Shen,et al.  Probing the photoluminescence properties of gold nanoclusters by fluorescence lifetime correlation spectroscopy. , 2013, The Journal of chemical physics.

[2]  G. Pasparakis.  Light-induced generation of singlet oxygen by naked gold nanoparticles and its implications to cancer cell phototherapy. , 2013, Small.

[3]  V. Biju,et al.  Singlet-oxygen-sensitizing near-infrared-fluorescent multimodal nanoparticles. , 2013, Angewandte Chemie.

[4]  C. Chiang,et al.  Morphology dependent photosensitization and formation of singlet oxygen (1Δg) by gold and silver nanoparticles and its application in cancer treatment. , 2013, Journal of materials chemistry. B.

[5]  R. Jin,et al.  Stable Au25(SR)18/TiO2 Composite Nanostructure with Enhanced Visible Light Photocatalytic Activity , 2013 .

[6]  Daniella Yeheskely-Hayon,et al.  High levels of reactive oxygen species in gold nanoparticle-targeted cancer cells following femtosecond pulse irradiation , 2013, Scientific Reports.

[7]  Wensheng Yan,et al.  Surface facet of palladium nanocrystals: a key parameter to the activation of molecular oxygen for organic catalysis and cancer treatment. , 2013, Journal of the American Chemical Society.

[8]  Xiaolan Chen,et al.  Photothermally enhanced photodynamic therapy based on mesoporous Pd@Ag@mSiO2 nanocarriers. , 2013, Journal of materials chemistry. B.

[9]  Uzi Landman,et al.  Au(67)(SR)(35) nanomolecules: characteristic size-specific optical, electrochemical, structural properties and first-principles theoretical analysis. , 2013, The journal of physical chemistry. A.

[10]  Douglas R. Kauffman,et al.  Photomediated Oxidation of Atomically Precise Au25(SC2H4Ph)18(-) Nanoclusters. , 2013, The journal of physical chemistry letters.

[11]  Peter Gölitz,et al.  Cover Picture: Champagne and Fireworks: Angewandte Chemie Celebrates Its Birthday (Angew. Chem. Int. Ed. 1/2013) , 2013 .

[12]  U. Landman,et al.  Total structure and electronic properties of the gold nanocrystal Au36(SR)24. , 2012, Angewandte Chemie.

[13]  R. Jin,et al.  Gold nanocluster-catalyzed selective oxidation of sulfide to sulfoxide. , 2012, Nanoscale.

[14]  Somen Mondal,et al.  Protein-templated gold nanoclusters: size dependent inversion of fluorescence emission in the presence of molecular oxygen. , 2012, Nanoscale.

[15]  X. Wen,et al.  Fluorescence Dynamics in BSA-Protected Au25 Nanoclusters , 2012 .

[16]  Frederico M. Pimenta,et al.  Singlet-oxygen-mediated cell death using spatially-localized two-photon excitation of an extracellular sensitizer. , 2012, The journal of physical chemistry. B.

[17]  K. Ishii.  Functional singlet oxygen generators based on phthalocyanines , 2012 .

[18]  L. Chao,et al.  Controlled growth of molecularly pure Au 25 (SR) 18 and Au 38 (SR) 24 nanoclusters from the same polydispersed crude product , 2012 .

[19]  Jaehoon Jung,et al.  Ligand effects on the stability of thiol-stabilized gold nanoclusters: Au25(SR)18(-), Au38(SR)24, and Au102(SR)44. , 2012, Nanoscale.

[20]  R. Jin,et al.  Water-soluble Au25(Capt)18 nanoclusters: synthesis, thermal stability, and optical properties. , 2012, Nanoscale.

[21]  S. Xie,et al.  Enhancement in Aerobic Alcohol Oxidation Catalysis of Au25 Clusters by Single Pd Atom Doping , 2012 .

[22]  Zhikun Wu,et al.  Quantum sized gold nanoclusters with atomic precision. , 2012, Accounts of chemical research.

[23]  Y. Negishi,et al.  Synthesis and the Origin of the Stability of Thiolate-Protected Au130 and Au187 Clusters. , 2012, Journal of Physical Chemistry Letters.

[24]  Xiu Shen,et al.  In vivo renal clearance, biodistribution, toxicity of gold nanoclusters. , 2012, Biomaterials.

[25]  D. A. Russell,et al.  Insights into the Mechanism of Quantum Dot-Sensitized Singlet Oxygen Production for Photodynamic Therapy , 2012 .

[26]  John F. Callan,et al.  Water soluble quantum dots as hydrophilic carriers and two-photon excited energy donors in photodynamic therapy , 2012 .

[27]  Michael R Hamblin,et al.  Can nanotechnology potentiate photodynamic therapy? , 2012, Nanotechnology reviews.

[28]  T. Tsukuda.  Toward an Atomic-Level Understanding of Size-Specific Properties of Protected and Stabilized Gold Clusters , 2012 .

[29]  Ruslan I. Dmitriev,et al.  Optical probes and techniques for O2 measurement in live cells and tissue , 2012, Cellular and Molecular Life Sciences.

[30]  K. Hwang,et al.  Metal nanoparticles sensitize the formation of singlet oxygen. , 2011, Angewandte Chemie.

[31]  T. Bürgi,et al.  Size exclusion chromatography for semipreparative scale separation of Au38(SR)24 and Au40(SR)24 and larger clusters. , 2011, Analytical chemistry.

[32]  D. Evanko.  The right chromophore for the job , 2011, Nature Methods.

[33]  A. Dass,et al.  Au36(SPh)23 nanomolecules. , 2011, Journal of the American Chemical Society.

[34]  R. Kornberg,et al.  Electronic and vibrational signatures of the Au102(p-MBA)44 cluster. , 2011, Journal of the American Chemical Society.

[35]  D. Bushnell,et al.  Synthesis and characterization of Au102(p-MBA)44 nanoparticles. , 2011, Journal of the American Chemical Society.

[36]  V. Sée,et al.  Inflicting controlled nonthermal damage to subcellular structures by laser-activated gold nanoparticles. , 2010, Nano letters.

[37]  J. Limtrakul,et al.  MALDI Mass Analysis of 11 kDa Gold Clusters Protected by Octadecanethiolate Ligands , 2010 .

[38]  Peter R Ogilby,et al.  Singlet oxygen: there is indeed something new under the sun. , 2010, Chemical Society reviews.

[39]  Joseph F. Parker,et al.  The story of a monodisperse gold nanoparticle: Au25L18. , 2010, Accounts of chemical research.

[40]  R. Jin,et al.  On the ligand's role in the fluorescence of gold nanoclusters. , 2010, Nano letters.

[41]  R. Jin,et al.  Total structure determination of thiolate-protected Au38 nanoparticles. , 2010, Journal of the American Chemical Society.

[42]  Elżbieta Wojaczyńska,et al.  Enantioselective synthesis of sulfoxides: 2000-2009. , 2010, Chemical reviews.

[43]  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.

[44]  R. Jin,et al.  Thiolate-Protected Au24(SC2H4Ph)20 Nanoclusters: Superatoms or Not? , 2010 .

[45]  Shuming Nie,et al.  Semiconductor nanocrystals: structure, properties, and band gap engineering. , 2010, Accounts of chemical research.

[46]  R. Jin,et al.  Atomically precise Au25(SR)18 nanoparticles as catalysts for the selective hydrogenation of alpha,beta-unsaturated ketones and aldehydes. , 2010, Angewandte Chemie.

[47]  Gang Zheng,et al.  Activatable photosensitizers for imaging and therapy. , 2010, Chemical reviews.

[48]  R. Jin,et al.  Size-focusing synthesis, optical and electrochemical properties of monodisperse Au38(SC2H4Ph)24 nanoclusters. , 2009, ACS nano.

[49]  R. Murray,et al.  Electrospray ionization mass spectrometry of intrinsically cationized nanoparticles, [Au(144/146)(SC(11)H(22)N(CH(2)CH(3))(3)(+))(x)(S(CH(2))(5)CH(3))(y)](x+). , 2009, Journal of the American Chemical Society.

[50]  R. Jin,et al.  Controlling nanoparticles with atomic precision: the case of Au144(SCH2CH2Ph)60. , 2009, Nano letters.

[51]  Asantha C. Dharmaratne,et al.  Nanocluster size evolution studied by mass spectrometry in room temperature Au25(SR)18 synthesis. , 2009, Journal of the American Chemical Society.

[52]  T. Tachikawa,et al.  Photochemical reactivity of gold clusters: dependence on size and spin multiplicity. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[53]  R. Jin,et al.  Thiolate-protected Au(20) clusters with a large energy gap of 2.1 eV. , 2009, Journal of the American Chemical Society.

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

[55]  Z. Marković,et al.  Biomedical potential of the reactive oxygen species generation and quenching by fullerenes (C60). , 2008, Biomaterials.

[56]  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.

[57]  R. Jin,et al.  Correlating the crystal structure of a thiol-protected Au25 cluster and optical properties. , 2008, Journal of the American Chemical Society.

[58]  T. Nyokong,et al.  Generation of singlet oxygen via the composites of water-soluble thiol-capped CdTe quantum dots-sulfonated aluminum phthalocyanines. , 2008, The journal of physical chemistry. B.

[59]  R. Murray,et al.  Crystal structure of the gold nanoparticle [N(C8H17)4][Au25(SCH2CH2Ph)18]. , 2008, Journal of the American Chemical Society.

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

[61]  Pablo D. Jadzinsky,et al.  Structure of a Thiol Monolayer-Protected Gold Nanoparticle at 1.1 Å Resolution , 2007, Science.

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

[63]  Shimon Weiss,et al.  Singlet oxygen production by Peptide-coated quantum dot-photosensitizer conjugates. , 2007, Journal of the American Chemical Society.

[64]  Robert M Dickson,et al.  Highly fluorescent noble-metal quantum dots. , 2007, Annual review of physical chemistry.

[65]  M. Wainwright,et al.  Phenothiazinium derivatives for pathogen inactivation in blood products. , 2007, Journal of photochemistry and photobiology. B, Biology.

[66]  G. Buettner,et al.  Ascorbate Reacts with Singlet Oxygen to Produce Hydrogen Peroxide , 2006, Photochemistry and photobiology.

[67]  Jia He,et al.  Time-dependent photoluminescence blue shift of the quantum dots in living cells: effect of oxidation by singlet oxygen. , 2006, Journal of the American Chemical Society.

[68]  Eduarda Fernandes,et al.  Fluorescence probes used for detection of reactive oxygen species. , 2005, Journal of biochemical and biophysical methods.

[69]  M. Fujii,et al.  Silicon Nanocrystals: Photosensitizers for Oxygen Molecules , 2005 .

[70]  Michael J. Hall,et al.  Supramolecular photonic therapeutic agents. , 2005, Journal of the American Chemical Society.

[71]  Katsuyuki Nobusada,et al.  Glutathione-protected gold clusters revisited: bridging the gap between gold(I)-thiolate complexes and thiolate-protected gold nanocrystals. , 2005, Journal of the American Chemical Society.

[72]  Zhivko Zhelev,et al.  Quantum dots as photosensitizers? , 2004, Nature Biotechnology.

[73]  William M Gallagher,et al.  In vitro demonstration of the heavy-atom effect for photodynamic therapy. , 2004, Journal of the American Chemical Society.

[74]  Zhivko Zhelev,et al.  Quantum dot anti-CD conjugates: Are they potential photosensitizers or potentiators of classical photosensitizing agents in photodynamic therapy of cancer? , 2004 .

[75]  M. Fujii,et al.  Chemical reaction mediated by excited states of Si nanocrystals - Singlet oxygen formation in solution , 2004 .

[76]  Ruomei Gao,et al.  Nanomaterials and singlet oxygen photosensitizers: potential applications in photodynamic therapy , 2004 .

[77]  F. Elisei,et al.  Electron transfer and singlet oxygen mechanisms in the photooxygenation of dibutyl sulfide and thioanisole in MeCN sensitized by N-methylquinolinium tetrafluoborate and 9,10-dicyanoanthracene. The probable involvement of a thiadioxirane intermediate in electron transfer photooxygenations. , 2003, Journal of the American Chemical Society.

[78]  Xiaobo Chen,et al.  Semiconductor quantum dots for photodynamic therapy. , 2003, Journal of the American Chemical Society.

[79]  Yukihiro Goda,et al.  Active oxygen species generated from photoexcited fullerene (C60) as potential medicines: O2-* versus 1O2. , 2003, Journal of the American Chemical Society.

[80]  N. Khiar,et al.  Recent developments in the synthesis and utilization of chiral sulfoxides. , 2003, Chemical reviews.

[81]  Reinhard Schmidt,et al.  Physical mechanisms of generation and deactivation of singlet oxygen. , 2003, Chemical reviews.

[82]  M. DeRosa.  Photosensitized singlet oxygen and its applications , 2002 .

[83]  D. A. Russell,et al.  Generation of Cytotoxic Singlet Oxygen via Phthalocyanine-Stabilized Gold Nanoparticles: A Potential Delivery Vehicle for Photodynamic Therapy , 2002 .

[84]  Robert L. Whetten,et al.  Visible to Infrared Luminescence from a 28-Atom Gold Cluster , 2002 .

[85]  W. Dunlap,et al.  Singlet oxygen from irradiated titanium dioxide and zinc oxide. , 2000, Methods in enzymology.

[86]  F. Jensen,et al.  Reaction of Organic Sulfides with Singlet Oxygen. A Revised Mechanism , 1998 .

[87]  K. Ishiguro,et al.  Mechanism of Sulfone Formation in the Reaction of Sulfides and Singlet Oxygen: Intermediacy of S-Hydroperoxysulfonium Ylide , 1996 .

[88]  James R. Sheats,et al.  Singlet Oxygen as a Reactive Intermediate in the Photodegradation of an Electroluminescent Polymer , 1995 .

[89]  R. Tsien,et al.  Fluorescence photooxidation with eosin: a method for high resolution immunolocalization and in situ hybridization detection for light and electron microscopy , 1994, The Journal of cell biology.

[90]  J. Barber,et al.  Isolated photosynthetic reaction center of photosystem II as a sensitizer for the formation of singlet oxygen. Detection and quantum yield determination using a chemical trapping technique. , 1994, The Journal of biological chemistry.

[91]  M. Karnovsky,et al.  The DAB-Mn++ cytochemical method revisited: validation of specificity for superoxide. , 1993, The journal of histochemistry and cytochemistry : official journal of the Histochemistry Society.

[92]  A. Nikolov,et al.  Dispersion stability due to structural contributions to the particle interaction as probed by thin liquid film dynamics , 1992 .

[93]  C. Foote.  DEFINITION OF TYPE I and TYPE II PHOTOSENSITIZED OXIDATION , 1991, Photochemistry and photobiology.

[94]  J. Kanofsky,et al.  QUENCHING OF SINGLET OXYGEN BY HUMAN PLASMA , 1990, Photochemistry and photobiology.

[95]  C. Foote,et al.  Chemistry of singlet oxygen. 45. Mechanism of the photooxidation of sulfides , 1983 .

[96]  B. Stevens,et al.  Photoperoxidation of unsaturated organic molecules. 19. 1,3-Diphenylisobenzofuran as sensitizer and inhibitor , 1981 .

[97]  Ahsan Khan.  Theory of electron transfer generation and quenching of singlet oxygen [1.SIGMA.g+ and 1.DELTA.g] by superoxide anion. The role of water in the dismutation of superoxide anion , 1977 .

[98]  Y. Lion,et al.  New method of detecting singlet oxygen production , 1976, Nature.

[99]  C. Foote,et al.  Chemistry of superoxide ion. III. Quenching of singlet oxygen , 1976 .

[100]  P. Merkel,et al.  Radiationless decay of singlet molecular oxygen in solution. Experimental and theoretical study of electronic-to-vibrational energy transfer , 1972 .

[101]  P. Merkel,et al.  KINETIC PROPERTIES OF THE TRIPLET STATES OF METHYLENE BLUE AND OTHER PHOTOSENSITIZING DYES , 1972, Photochemistry and photobiology.

[102]  E. Corey,et al.  A Study of the Peroxidation of Organic Compounds by Externally Generated Singlet Oxygen Molecules , 1964 .

[103]  R. S. Mulliken,et al.  Interpretation of the Atmospheric Oxygen Bands; Electronic Levels of the Oxygen Molecule , 1928, Nature.