%0 Journal Article %1 Heilemann2006 %A Heilemann, Mike %A Kasper, Robert %A Tinnefeld, Philip %A Sauer, Markus %C 1155 16TH ST, NW, WASHINGTON, DC 20036 USA %D 2006 %I AMER CHEMICAL SOC %J JOURNAL OF THE AMERICAN CHEMICAL SOCIETY %K sauer mike %N 51 %P 16864-16875 %T Dissecting and reducing the heterogeneity of excited-state energy transport in DNA-Based photonic wires %U http://dx.doi.org/10.1021/ja065585x %V 128 %X Molecular photonic wires are one-dimensional representatives of a family of nanoscale molecular devices that transport excited-state energy over considerable distances in analogy to optical waveguides in the far-field. In particular, the design and synthesis of such complex supramolecular devices is challenging concerning the desired homogeneity of energy transport. On the other hand, novel optical techniques are available that permit direct investigation of heterogeneity by studying one device at a time. In this article, we describe our efforts to synthesize and study DNA-based molecular photonic wires that carry several chromophores arranged in an energetic downhill cascade and exploit fluorescence resonance energy transfer to convey excited-state energy. The focus of this work is to understand and control the heterogeneity of such complex systems, applying single-molecule fluorescence spectroscopy (SMFS) to dissect the different sources of heterogeneity, i.e., chemical heterogeneity and inhomogeneous broadening induced by the nanoenvironment. We demonstrate that the homogeneity of excited-state energy transport in DNA-based photonic wires is dramatically improved by immobilizing photonic wires in aqueous solution without perturbation by the surface. In addition, our study shows that the in situ construction of wire molecules, i.e., the stepwise hybridization of differently labeled oligonucleotides on glass cover slides, further decreases the observed heterogeneity in overall energy-transfer efficiency. The developed strategy enables efficient energy transfer between up to five chromophores in the majority of molecules investigated along a distance of similar to 14 nm. Finally, we used multiparameter SMFS to analyze the energy flow in photonic wires in more detail and to assign residual heterogeneity under optimized conditions in solution to different leakages and competing energy-transfer processes.

@article{Heilemann2006, abstract = {Molecular photonic wires are one-dimensional representatives of a family of nanoscale molecular devices that transport excited-state energy over considerable distances in analogy to optical waveguides in the far-field. In particular, the design and synthesis of such complex supramolecular devices is challenging concerning the desired homogeneity of energy transport. On the other hand, novel optical techniques are available that permit direct investigation of heterogeneity by studying one device at a time. In this article, we describe our efforts to synthesize and study DNA-based molecular photonic wires that carry several chromophores arranged in an energetic downhill cascade and exploit fluorescence resonance energy transfer to convey excited-state energy. The focus of this work is to understand and control the heterogeneity of such complex systems, applying single-molecule fluorescence spectroscopy (SMFS) to dissect the different sources of heterogeneity, i.e., chemical heterogeneity and inhomogeneous broadening induced by the nanoenvironment. We demonstrate that the homogeneity of excited-state energy transport in DNA-based photonic wires is dramatically improved by immobilizing photonic wires in aqueous solution without perturbation by the surface. In addition, our study shows that the in situ construction of wire molecules, i.e., the stepwise hybridization of differently labeled oligonucleotides on glass cover slides, further decreases the observed heterogeneity in overall energy-transfer efficiency. The developed strategy enables efficient energy transfer between up to five chromophores in the majority of molecules investigated along a distance of similar to 14 nm. Finally, we used multiparameter SMFS to analyze the energy flow in photonic wires in more detail and to assign residual heterogeneity under optimized conditions in solution to different leakages and competing energy-transfer processes.}, added-at = {2011-03-01T10:57:13.000+0100}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, affiliation = {Tinnefeld, P (Reprint Author), Univ Bielefeld, Appl Laser Phys \& Laser Spect, Univ Str 25, D-33615 Bielefeld, Germany. Univ Bielefeld, Appl Laser Phys \& Laser Spect, D-33615 Bielefeld, Germany.}, author = {Heilemann, Mike and Kasper, Robert and Tinnefeld, Philip and Sauer, Markus}, author-email = {tinnefeld@physik.uni-bielefeld.de}, biburl = {https://www.bibsonomy.org/bibtex/26e49b93293a1c61e8c77cf698ffbb524/reichert}, cited-references = {BARBARA PF, 2005, ACCOUNTS CHEM RES, V38, P602, DOI 10.1021/ar040141w. BECKER K, 2006, J AM CHEM SOC, V128, P6468, DOI 10.1021/ja0609405. BECKER K, 2006, J AM CHEM SOC, V128, P680, DOI 10.1021/ja056469h. BOHMER M, 2003, J OPT SOC AM B, V20, P554. CLEGG RM, 1992, METHOD ENZYMOL, V211, P353. COTLET M, 2005, J AM CHEM SOC, V127, P2760. DENIZ AA, 1999, P NATL ACAD SCI USA, V96, P3670. DESCHRYVER FC, 2005, ACCOUNTS CHEM RES, V38, P514, DOI 10.1021/ar040126r. DICKSON RM, 1996, MOL CRYST LIQ CRYS A, V291, P31. DIETRICH A, 2002, REV MOL BIOTECHNOL, V82, P211. DITTRICH PS, 2001, APPL PHYS B-LASERS O, V73, P829. EDMAN L, 1996, P NATL ACAD SCI USA, V93, P6710. EGGELING C, 1998, P NATL ACAD SCI USA, V95, P1556. EGGELING C, 2006, J PHYS CHEM A, V110, DOI 10.1021/jp054581w. FORSTER T, 1948, M PHYS, V2, P55. FUNATSU T, 1995, NATURE, V374, P555. GARCIAPARAJO MF, 2005, CHEMPHYSCHEM, V6, P819, DOI 10.1002/cphc.200400630. GROLL J, 2004, J AM CHEM SOC, V126, P4234, DOI 10.1021/ja0318028. GUST D, 2001, ACCOUNTS CHEM RES, V34, P40, DOI 10.1021/ar9801301. HA T, 1996, PHYS REV LETT, V77, P3979. HA T, 2001, METHODS, V25, P78. HA TJ, 1999, CHEM PHYS, V247, P107. HARAN G, 2003, J PHYS-CONDENS MAT, V15, R1291. HEILEMANN M, UNPUB. HEILEMANN M, 2004, J AM CHEM SOC, V126, P6514, DOI 10.1021/ja049351u. HEINLEIN T, 2003, J PHYS CHEM B, V107, P7957, DOI 10.1021/jp0348068. HEINLEIN T, 2005, CHEMPHYSCHEM, V6, P949, DOI 10.1002/cphc.200400622. HERNANDO J, 2004, ANGEW CHEM INT EDIT, V43, P4045, DOI 10.1002/anie.200453745. HOEBEN FJM, 2005, J CHEM REV, V105, P1491. HOFKENS J, 2000, J AM CHEM SOC, V122, P9278. HOFKENS J, 2003, P NATL ACAD SCI USA, V100, P13146, DOI 10.1073/pnas.2235805100. HOLMAN MW, 2003, J AM CHEM SOC, V125, P12649, DOI 10.1021/ja0343104. HUBNER CG, 2004, J CHEM PHYS, V120, P10867, DOI 10.1063/1.1760492. HUSER T, 2000, P NATL ACAD SCI USA, V97, P11187. KIM D, 2004, ACCOUNTS CHEM RES, V37, P735, DOI 10.1021/ar030242e. KIM J, 2006, NUCLEIC ACIDS RES, V34, P2516, DOI 10.1093/nar/gkl221. KIM YH, 2001, J AM CHEM SOC, V123, P76. LU HP, 1997, NATURE, V385, P143. MORGAN MA, 2005, BIOPHYS J, V89, P2588, DOI 10.1529/biophysj.105.067728. MOSTEIRO GS, J PHYS CHEM B. NEUWEILER H, 2005, P NATL ACAD SCI USA, V102, P16650, DOI 10.1073/pnas.0507351102. NORMAN DG, 2000, BIOCHEMISTRY-US, V39, P6317. OKUMUS B, 2004, BIOPHYS J, V87, P2798, DOI 10.1529/biophysj.104.045971. PAL P, 2005, BIOPHYS J, V89, P11. PARK M, 2005, J AM CHEM SOC, V127, P15201, DOI 10.1021/ja0544861. PIESTERT O, 2003, NANO LETT, V3, P979, DOI 10.1021/nl0341988. ROTHWELL PJ, 2003, P NATL ACAD SCI USA, V100, P1655, DOI 10.1073/pnas.0434003100. SAUER M, 1998, CHEM PHYS LETT, V284, P153. SAUER M, 2003, ANGEW CHEM INT EDIT, V42, P1790, DOI 10.1002/anie.200201611. SCHINDLER F, 2004, P NATL ACAD SCI USA, V101, P14695, DOI 10.1073/pnas.0403325101. SCHOLES GD, 2003, ANNU REV PHYS CHEM, V54, P57, DOI 10.1146/annurev.physchem.540.11002.103746. SCHULER B, 2005, P NATL ACAD SCI USA, V102, P2754, DOI 10.1073/pnas.0408164102. SCHWARTZ BJ, 2003, ANNU REV PHYS CHEM, V54, P141, DOI 10.1146/annurev.physchem.54.011002.103811. SEIDEL CAM, 1996, J PHYS CHEM-US, V100, P5541. TALAGA DS, 2000, P NATL ACAD SCI USA, V97, P13021. TINNEFELD P, 2001, J PHYS CHEM A, V105, P7989. TINNEFELD P, 2002, J AM CHEM SOC, V124, P14310, DOI 10.1021/ja027343c. TINNEFELD P, 2003, J PHYS CHEM A, V107, P323, DOI 10.1021/jp026565u. TINNEFELD P, 2004, CHEMPHYSCHEM, V5, P1786, DOI 10.1002/cphc.200400325. TINNEFELD P, 2004, RECENT RES DEV PHYS, V7, P95. TINNEFELD P, 2005, ANGEW CHEM INT EDIT, V44, P2642, DOI 10.1002/anie.200300647. TINNEFELD P, 2005, CHEMPHYSCHEM, V6, P217, DOI 10.1002/cphc.200400513. TURRO NJ, 1978, MODERN MOL PHOTOCHEM, P628. VAMOSI G, 1996, BIOPHYS J, V71, P972. VANDENBOUT DA, 1997, SCIENCE, V277, P1074. WAGNER RW, 1994, J AM CHEM SOC, V116, P9759. WESTON KD, 2002, ANAL CHEM, V74, P5342, DOI 10.1021/ac025730z. WILLARD DM, 2006, ANAL BIOANAL CHEM, V384, P564, DOI 10.1007/s00216-005-0250-z. YEOW EKL, 2006, J PHYS CHEM A, V110, P1726, DOI 10.1021/jp055496r. YING LM, 1998, J PHYS CHEM B, V102, P10399. YU J, 2000, SCIENCE, V289, P1327. ZONDERVAN R, 2003, J PHYS CHEM A, V107, P6770, DOI 10.1021/jp034723r. ZUKER M, 2003, NUCLEIC ACIDS RES, V31, P3406, DOI 10.1093/nar/gkg595.}, doc-delivery-number = {118KQ}, groups = {public}, interhash = {3b7c18db86664f77f9c43cbe31ce08a8}, intrahash = {6e49b93293a1c61e8c77cf698ffbb524}, issn = {0002-7863}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, journal-iso = {J. Am. Chem. Soc.}, keywords = {sauer mike}, keywords-plus = {SINGLE-MOLECULE FLUORESCENCE; CONJUGATED POLYMER-MOLECULES; ELECTRON-TRANSFER; PORPHYRIN ARRAYS; SPECTROSCOPY; DYNAMICS; MICROSCOPY; DYE; EXCITATION; SYSTEM}, language = {English}, month = {DEC 27}, number = 51, number-of-cited-references = {73}, pages = {16864-16875}, publisher = {AMER CHEMICAL SOC}, subject-category = {Chemistry, Multidisciplinary}, times-cited = {28}, timestamp = {2011-03-09T14:16:39.000+0100}, title = {Dissecting and reducing the heterogeneity of excited-state energy transport in DNA-Based photonic wires}, type = {Article}, unique-id = {ISI:000242941600092}, url = {http://dx.doi.org/10.1021/ja065585x}, username = {reichert}, volume = 128, year = 2006 }