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Spectroscopic Characterization of Plasma – Chemically Functionalized and Fluorophore-Labeled Polymer Surfaces

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Reviews in Fluorescence 2008

Part of the book series: Reviews in Fluorescence 2008 ((RFLU,volume 2008))

Abstract

The potential of spectrofluorometry and fluorescence microscopy for the characterization and quantification of different functionalities like OH and NH2 groups at plasma-chemically modified polymer surfaces is assessed using traditional reactive dyes such as dansyl derivatives and a sophisticated VIS-excitable chromogenic and fluorogenic pyrylium label showing binding-induced spectral and intensity changes in absorption and emission. Aiming at an improved fluorometric surface analysis, based upon these measurements, several sources of uncertainty inherent to fluorescence measurements are illustrated ranging from environment-dependent dye absorption and emission features over spectral correction and nonspecific adsorption to the critical influence of label choice on the measured background. Solutions to these drawbacks are given thereby underlining the potential of fluorometry for surface analysis.

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References

  1. A. De Mello, Plastic fantastic?, Lab Chip 2, 31 N–36 N (2002).

    Google Scholar 

  2. A. Piruska, I. Nikcevic, S. H. Lee, C. Ahn, W. R. Heinemann, P. A. Limbach, and C. J. Seliskar, The autofluorescence of plastic materials and chips measured under laser irradiation, Lab Chip 5, 1348–1354 (2005).

    Article  CAS  PubMed  Google Scholar 

  3. E. A. McArthur, T. Ye, J. P. Cross, S. Petoud, and E. Borguet, Fluorescence detection of surface-bound intermediates produced from UV photoreactivity of alkylsiloxane SAMs, J. Am. Chem. Soc. 126, 2260–2261 (2004).

    Article  CAS  PubMed  Google Scholar 

  4. T. Shimada, K. Aoki, T. Nakamura, N. Tokunaga, S. Inagaki, and T. Hayashi, Functionalization on silica gel with allylsilanes. A new method of covalent attachment of organic functional groups on silica gel, J. Am. Chem. Soc. 125, 4688–4689 (2003).

    Article  CAS  PubMed  Google Scholar 

  5. G. M. Harbers, K. Emoto, C. Greef, S. W. Metzger, H. N. Woodward, J. J. Mascali, D. W. Grainger, and M. J. Lochhead, Functionalized poly(ethylene glycol)-based bioassay surface chemistry that facilitates bio-immobilization and inhibits nonspecific protein, bacterial, and mammalian cell adhesion, Chem. Mater. 19, 4405–4414 (2007).

    Article  CAS  PubMed  Google Scholar 

  6. W. C. E. Schofield, J. McGettrick, T. J. Bradley, J. P. S. Badyal, and S. Przyborski, Rewritable DNA microarrays, J. Am. Chem. Soc. 128, 2280–2285 (2006).

    Article  CAS  PubMed  Google Scholar 

  7. J. Kang, L. Ding, F. Lü, S. Zhang, and Y. Fang, Dansyl-based fluorescent film sensor for nitroaromatics in aqueous solution, J. Phys. D Appl. Phys. 39, 5097–5102 (2006).

    Article  CAS  Google Scholar 

  8. B. K. Inamori, M. Kyo, K. Matsukawa, Y. Inoue, T. Sonoda, K. Tatematsu, K. Tanizawa, T. Mori, and Y. Kataya, Optimal surface chemistry for peptide immobilization in on-chip phosphorylation analysis, Anal. Chem. 80(3), 643–650 (2008).

    Article  CAS  PubMed  Google Scholar 

  9. D. Belder and M. Ludwig, Surface modification in microchip electrophoresis, Electrophoresis 24, 3595–3606 (2003).

    Article  CAS  PubMed  Google Scholar 

  10. A. Muck and S. Svatoš. Chemical modification of polymeric microchip devices, Talanta 74, 333–341 (2007).

    CAS  PubMed  Google Scholar 

  11. A. Holländer, Labelling techniques for the chemical analysis of polymer surfaces, Surf. Interface Anal. 36, 1023–1026 (2004).

    Article  Google Scholar 

  12. R. Mix, K. Hoffmann, U. Resch-Genger, R. Decker, and J. F. Friedrich, Covalent coupling of fluorophores to polymer surface-bonded functional groups, In: Polymer Surface Modification (Ed. K. L. Mittal), 4, 171–191 (2007).

    Google Scholar 

  13. C. Oehr, Plasma surface modification of polymers for biomedical use, Nucl. Instrum. Methods Phys. Res. B 208, 40–47 (2003).

    Article  CAS  Google Scholar 

  14. P. K. Chu, J. Y. Chen, L. P.Wang, and N. Huang, Plasma-surface modification of biomaterials, Mater. Sci. Eng. 36, 143–206 (2002).

    Article  Google Scholar 

  15. C. M. Chan, T. M. Ko, and H. Hiraoka, Polymer surface modification by plasmas and photons, Surf. Sci. Rep. 24, 1–54 (1996).

    Article  CAS  Google Scholar 

  16. P. Favia and R. de’Agostino, Plasma treatments and plasma deposition of polymers for biomedical applications, Surf. Coat. Technol. 98, 1102–1106 (1998).

    Article  CAS  Google Scholar 

  17. G. Ji, J. Fang, S. Cai, and G. Xue, Grafting onto the surface of plasma-modified fillers, Appl. Surf. Sci. 81, 63–68 (1994).

    Article  CAS  Google Scholar 

  18. F. Cheng, L. J. Gamble, D. W. Grainger, and D. G. Castner, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and principal component analysis of the hydrolysis, regeneration, and reactivity of N-hydroxysuccinimide-containing organic thin films, Anal. Chem. 79(22), 8781–8788 (2007).

    Article  CAS  PubMed  Google Scholar 

  19. C. Y. Lee, G. M. Harbers, D. W. Grainger, L. J. Gamble, and D. G. Castner, Fluorescence, XPS, and TOF-SIMS surface chemical state image analysis of DNA microarrays, J. Am. Chem. Soc. 129, 9429–9438 (2007).

    Article  CAS  PubMed  Google Scholar 

  20. X. Z. Song, B. Y. Xia, Y. Lasanajak, D. F. Smith, and R. D. Cummings, Quantifiable fluorescent glycan microarrays, Glycoconj. J. 25, 15–25 (2008).

    Article  CAS  PubMed  Google Scholar 

  21. D. J. Benesch, G. Hungerford, K. Suhling, C. Tregidgo, J. F. Mano, and R. L. Reis, Fluorescence probe techniques to monitor protein adsorption-induced conformation changes on biodegradable polymers, J. Colloid Interface Sci. 312, 193–200 (2007).

    Article  CAS  PubMed  Google Scholar 

  22. E. Z. Huang, H. Ji, J. W. Mays, and M. D. Dadmun, Understanding the grafting of telechelic polymers on a solid surface to form loops, Macromolecules 41, 1009–1018 (2007).

    Article  Google Scholar 

  23. A. Holländer, S. Kröpke, and F. Pippig, Chemical analysis of functionalized polymer surfaces, Surf. Interface Anal. 40, 379–385 (2008).

    Article  Google Scholar 

  24. P. Gong, G. M. Harbers, and D. W. Grainger, Multi-technique comparison of immobilized and hybridized oligonucleotide surface density on commercial amine-reactive microarray slides, Anal. Chem. 78(7), 2342–2351 (2006).

    Article  CAS  PubMed  Google Scholar 

  25. P. Gong, C. Y. Lee, L. J. Gamble, D. G. Castner, and D. W. Grainger, Hybridization behavior of mixed DNA/alkylthiol monolayers on gold: Characterization by surface plasmon resonance and 32P radiometric assay, Anal. Chem. 78(10), 3326–3334 (2006).

    Article  CAS  PubMed  Google Scholar 

  26. K. E. Sapsford, L. Berti, and I. L. Medintz, Materials for fluorescence resonance energy transfer analysis: Beyond traditional donor-acceptor combinations, Angew. Chem. Int. Ed. 45(28), 4562–4588 (2006).

    Article  CAS  Google Scholar 

  27. V. B. Ivanov, J. Behnisch, A. Holländer, F. Mehdorn, and H. Zimmermann, Determination of functional groups on polymer surfaces using fluorescence labelling, Surf. Interface Anal. 24, 257–262 (1996).

    Article  CAS  Google Scholar 

  28. S. R. Holmes-Farley and G. M. Whitesides, Fluorescence properties of dansyl groups covalently bonded to the surface of oxidatively functionalized low-density polyethylene film, Langmuir 2, 266–281 (1986).

    Article  CAS  Google Scholar 

  29. H. J. Griesser and R. C. Chatelier, Surface characterization of plasma polymers from amine, amide and alcohol monomers, J. Appl. Polym. Sci., Appl. Polym. Symp. 46, 361–384 (1990).

    Article  CAS  Google Scholar 

  30. C. Henneuse-Boxus , A. de Ro, P. Bertrand, and J. Marchand-Brynaert, Covalent attachment of fluorescence probes on the PEEK-OH film surface, Polymer 41, 2339–2348 (2000).

    Article  CAS  Google Scholar 

  31. L. Wang, A. K. Gaigalas, and Y. Reipa, Biotechniques 38, 127–132 (2005).

    Article  PubMed  Google Scholar 

  32. K. Hoffmann, U. Resch-Genger, R. Mix, and J. F. Friedrich, Fluorescence spectroscopic studies on plasma-chemically modified polymer surfaces with fluorophore-labeled functionalities, J. Fluoresc. 16, 441–448 (2006).

    Article  CAS  PubMed  Google Scholar 

  33. R. G. Nuzzo and G. Smolinsky, Preparation and characterization of functionalized polyethylene surfaces, Macromolecules 17, 1013–1019 (1984).

    Article  CAS  Google Scholar 

  34. G. Kühn, S. Weidner, R. Decker, A. Ghode, and J. F. Friedrich, Selective surface functionalization of polyolefins by plasma treatment followed by chemical reduction. Surf. Coat. Technol. 116–119, 796–801 (1999).

    Article  Google Scholar 

  35. J. Friedrich, G. Kühn, R. Mix, K. Hoffmann, and U. Resch-Genger, Tailoring of polymer surfaces with monotype functional groups of variable density using chemical and plasma chemical processes, Prog. Colloid Polym. Sci. 132, 62–71 (2006).

    Article  CAS  Google Scholar 

  36. R. P. Haugland, Ed., Handbook of Fluorescent Probes and Research Products, 9th ed.; Molecular Probes (2002).

    Google Scholar 

  37. W.T. Mason, Ed., Fluorescent and Luminescent Probes for Biological Activity, 2nd ed.; Academic Press, New York (1999).

    Google Scholar 

  38. V. Buschmann, K. D. Weston, and M. Sauer, Spectroscopic study and evaluation of red-absorbing fluorescent dyes, Bioconjug. Chem. 14, 195–204 (2003).

    Article  CAS  PubMed  Google Scholar 

  39. S. Dähne, U. Resch-Genger, O. S. Wolfbeis, Near-infrared dyes for high technology applications. NATO ASI Series, 3. Hightechnology – Vol. 52, Kluwer Academic Publishers, Dordrecht, The Netherlands, 1998.

    Google Scholar 

  40. Z. R. Grabowski, K. Rotkiewicz, and W. Rettig, Structural changes accompanying intramolecular electron transfer: Focus an twisted intramolecular charge transfer states and structures, Chem. Rev. 103(10), 3899–4031 (2003).

    Article  PubMed  Google Scholar 

  41. R. Mix, K. Hoffmann, H. J. Buschmann, J. F. Friedrich, and U. Resch-Genger, Coupling of fluorescence labels to plasma-chemically functionalized and cucurbituril modified surfaces, Vak. Forsch. Prax. 19, 31–37 (2007).

    Article  CAS  Google Scholar 

  42. B. K. Hoefelschweiger, A. Duerkop, and O. S. Wolfbeis, Novel type of general protein assay using a chromogenic and fluorogenic amine-reactive probe, Anal. Biochem. 344(1), 122–129 (2005).

    Article  CAS  PubMed  Google Scholar 

  43. S. Udenfriend, S. Stein, P. Böhlen, W. Dairman, W. Leimgruber, and M. Weigele, Fluorescamine: A reagent for assay of amino acids, peptides, proteins, and primary amines in the picomole range, Science 178, 871–872 (1972).

    Article  CAS  PubMed  Google Scholar 

  44. K. Hoffmann, R. Mix, U. Resch-Genger, and J. F. Friedrich, Monitoring of amino functionalities on plasma-chemically modified polypropylene supports with a chromogenic and fluorogenic pyrylium reporter, Langmuir 23, 8411–8416 (2007).

    Article  CAS  PubMed  Google Scholar 

  45. J. F. Friedrich, G. Kühn, R. Mix, and W. E. S. Unger, Formation of plasma polymer layers with functional groups of different type and density at polymer surfaces and their interaction with Al atoms, Polym. Process. Plasmas 1, 28–51 (2004).

    Article  CAS  Google Scholar 

  46. Y. Xing and E. Borguet, Specificity and sensitivity of fluorescence labeling of surface species, Langmuir 23, 684–688 (2007).

    Article  CAS  PubMed  Google Scholar 

  47. M. Mirenda, M. G. Lagorio, and E. San Roman, Photophysics on surfaces: Determination of absolute fluorescence quantum yields from reflectance spectra. Langmuir 20, 3690–3697 (2004).

    Article  CAS  PubMed  Google Scholar 

  48. K. Hoffmann, R. Mix, U. Resch-Genger, and J. F. Friedrich, Fluorescence measurements on functionalized polymer surfaces – problems and troubleshooting, Ann. N Y Acad. Sci. 1130(1), 28–34 (2008).

    Article  CAS  PubMed  Google Scholar 

  49. F. J. R. Lakowicz, Principles of Fluorescence Spectroscopy, 3nd edn.; Springer Science and Business, New York (2006).

    Google Scholar 

  50. B. Ren, F. Gao, Z. Tong, and Y.Yan, Solvent polarity scale on the fluorescence spectra of a dansyl monomer copolymerizable in aqueous media, Chem. Phys. Lett. 307, 55–61 (1999).

    Article  CAS  Google Scholar 

  51. J. Gonzalez-Benito, A. Aznar, and J. Baselga, Solvent and temperature Effects on Polymer-Coated Glass Fibers: Fluorescence of the Dansyl Moiety, J. Fluoresc. 11(4), 307–314 (2001).

    Article  CAS  Google Scholar 

  52. R. P. Haugland, Ed., The Handbook: A guide to fluorescent probes and labeling technologies, 10th ed. Invitrogen, Eugene, 2005.

    Google Scholar 

  53. J. E. Rasmussen, D. E. Bergbreiter, and G. M. Whitesides, Location and mobility of functional groups at the surface of oxidized, low-density polyethylene films, J. Am. Chem. Soc. 99(14), 4746–4756 (1977).

    Article  CAS  Google Scholar 

  54. M. Hennecke, I. Schneider, and J. Fuhrmann, Characterization of carboxylate sites in surface oxidized polyethylene films by fluorescence techniques, Eur. Polym. J. 22(12), 946–953 (1986).

    Article  Google Scholar 

  55. U. Resch-Genger, K. Hoffmann, W. Nietfeld, A. Engel, J. Neukammer, R. Nitschke, B. Ebert, and R. Macdonald, How to improve quality assurance in fluorometry: Fluorescence-inherent sources of error and suited fluorescence standards, J. Fluoresc. 15(3), 337–362 (2005), and references therein.

    Article  CAS  PubMed  Google Scholar 

  56. S. Nishiyama, M. Tajima, and Y. Yoshida, Polarized fluorescence of spin-coated polymeric thin films, J. Photopolym. Sci. Tech. 20(2), 257–264 (2007).

    Article  CAS  Google Scholar 

  57. U. Resch-Genger, D. Pfeifer, C. Monte, W. Pilz, A. Hoffmann, M. Spieles, K. Rurack, D. Taubert, B. Schoenberger, and P. Nording, Traceability in fluorometry: Part II. Spectral fluorescence standards. J. Fluoresc. 15, 325–346 (2005).

    Google Scholar 

  58. S. Ekgasit, G. Stengel, and W. Knoll, Concentration of dye-labeled nucleotides incorporated into DNA determined by surface plasmon resonance-surface plasmon fluorescence spectroscopy, Anal. Chem. 76, 4747–4755 (2004).

    Article  CAS  PubMed  Google Scholar 

  59. Y. Garini, B. J. Vermolen, and I. T. Young, From micro to nano: Recent advances in high-resolution microscopy, Curr. Opin. Biotechnol. 16, 3–12 (2005).

    Article  CAS  PubMed  Google Scholar 

  60. A. H. Nashat, M. Moronne, and M. Ferrari, Detection of functional groups and antibodies on microfabricated surfaces by confocal microscopy, Biotechnol. Bioeng. 60, 137–146 (1998).

    Article  CAS  PubMed  Google Scholar 

  61. S. Bratskaya, D. Marinin, M. Nitschke, D. Pleul, S. Schwarz, and F. Simon, Polypropylene surface functionalization with chitosan, J. Adhes. Sci. Technol. 18, 1173–1186 (2004).

    Article  CAS  Google Scholar 

  62. J. E. Noble, L. Wang, K. D. Cole, and A. K. Gaigalas, The Effect of overhanging nucleotides on fluorescence properties of hybridizing oligonucleotides labeled with Alexa-488 and FAM fluorophores, Biophys. Chem. 113, 255–263 (2005).

    Article  CAS  PubMed  Google Scholar 

  63. B. K. Wetzl, S. M. Yarmolouk, D. B. Craig, and O. S. Wolfbeis, Chameleon labels for staining and quantifying proteins, Angew. Chem. Int. Ed. 43, 5400–5402 (2004).

    Article  CAS  Google Scholar 

  64. A. Papra, H. G. Hicke, and D. Paul, Synthesis of peptides onto the surface of poly(ethylene terephthalate) particle track membranes, J. Appl. Polym. Sci. 74, 1669–1674 (1999).

    Article  CAS  Google Scholar 

  65. E. Brynda, J. Drobnik, J. Vacik, and J. Kalal, Protein sorption on polymer surfaces measured by fluorescence labels Biomed. Mater. Res. 12, 55–65 (1978).

    Article  CAS  Google Scholar 

  66. S. M. Yarmolouk, A. M. Kostenko, and I. Y. Dubey, Interaction of cyanine dyes with nucleic acids. Part 19: New method for the covalent labeling of oligonucleotides with pyrylium cyanine dyes, Bioorg. Med. Chem. Lett. 10, 2201–2204 (2000).

    Article  Google Scholar 

  67. J. L. Bricks, J. L. Slominski, M. A. Kudinova, A. I. Tolmachev, K. Rurack, U. Resch-Genger, and W. Rettig, Syntheses and photophysical properties of a series of cation-sensitive polymethine and styryl dyes, J. Photochem. Photobiol. A 132, 193–208 (2000).

    Article  CAS  Google Scholar 

  68. B. Garcia-Acosta, M. Comes, J. L. Bricks, M. K. Kudinova, V. V. Kurdyukov, A. I. Tolmachev, A. B. Descalzo, M. D. Marcos, R. Martinez-Manez, A. Morno, F. Sancenon, L. A. Villaescusa, K. Rurack, J. M. Barat, I. Escriche, and P. Amoros, Sensory hybrid host materials for the selective chromo-fluorogenic detection of biogenic amines, Chem. Commun. 2239–2241 (2006).

    Google Scholar 

  69. H. Hachisako and R. Murakami, Intense fluorescence-inducing amphiphile in cationic dyes and its applicability, Chem. Commun. 1073–1075 (2006).

    Google Scholar 

  70. C. Zhang, N. Luo, and D. E. Hirt, Penetration behavior and subsurface grafting of dansyl cadaverine and polyethylene glycol (PEG) derivatives in poly(ethylene-co-acrylic acid) (EAA) film, Polymer 46, 9257–9264 (2005).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Federal Institute for Materials Research and Testing (BAM), Richard-Willstaetter-Str. 11, D-12489, Berlin, Germany

    Katrin Hoffmann, Renate Mix & Joerg F. Friedrich

  2. Working Group Fluorescence Spectroscopy, Department I, BAM Federal Institute for Materials Research and Testing, Richard-Willstaetter-Str. 11, D-12489, Berlin, Germany

    Ute Resch-Genger

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  1. Katrin Hoffmann
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  2. Renate Mix
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  4. Ute Resch-Genger
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Correspondence to Ute Resch-Genger .

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  1. Institute of Fluorescence, University of Maryland, 701 E. Pratt St., Suites 3017-21, Baltimore, MD, 21202, USA

    Chris D. Geddes

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Hoffmann, K., Mix, R., Friedrich, J.F., Resch-Genger, U. (2010). Spectroscopic Characterization of Plasma – Chemically Functionalized and Fluorophore-Labeled Polymer Surfaces. In: Geddes, C.D. (eds) Reviews in Fluorescence 2008. Reviews in Fluorescence 2008, vol 2008. Springer, New York, NY. https://doi.org/10.1007/978-1-4419-1260-2_6

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