Heavy-atom quenching of 9-ethylcarbazole in heterogeneous matrice

Rochester Institute of Technology RIT Scholar Works Theses Thesis/Dissertation Collections 8-1-2001 Heavy-atom quenching of 9-ethylcarbazole in heterogeneous matrices: Micelles and latexes Paul Conrow Follow this and additional works at: http://scholarworks.rit.edu/theses Recommended Citation Conrow, Paul, "Heavy-atom quenching of 9-ethylcarbazole in heterogeneous matrices: Micelles and latexes" (2001) Thesis Rochester Institute of Technology Accessed from This Thesis is brought to you for free and open access by the Thesis/Dissertation Collections at RIT Scholar Works It has been accepted for inclusion in Theses by an authorized administrator of RIT Scholar Works For more information, please contact ritscholarworks@rit.edu Heavy-atom Quenching of 9-Ethylcarbazole in Heterogeneous Matrices: Micelles and Latexes Paul D Conrow August 2001 A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Chemistry Approved: Andreas Langner Thesis Advisor T C Morrill Department Head Department of Chemistry Rochester Institute of Technology Rochester, NY 14623-5603 Copyright Release Form Heavy-atom Quenching of 9-Ethylcarbazole in Heterogeneous Matrices: Micelles and Latexes I, Paul D Conrow, hereby grant permission to Wallace Memorial Library of the Rochester Institute of Technology, to reproduce my thesis in whole or in part Any reproduction will not be for commercial use or profit Signature: _ Abstract The fluorescence quenching of 9-ethylcarbazole was studied heterogeneous dispersions A heavy-atom quencher, 4-iodotoluene, in solution and was used to quench the fluorescence of 9-ethylcarbazole Polymer analogs of 9-ethylcarbazole and 4-iodotoluene were incorporated into separate were carried out with non-polymer and solutions and solutions created latex dispersions The diffusion high local was latex-bound 20-1000 times of analytes concentrations of global concentrations remained latex solutions, phase of species and methacrylate)-co-vinylcarbazole] At SDS 0.008 M, quencher concentration of latex solutions x micellar heterogeneous quencher, matrices while the relatively low The fluorescence quenching in latex solutions of poly[(methyl concentrations of experiments than in homogeneous more efficient fluorescing quenching Quenching in analytes into the dispersed the and a Stern- Volmer slope of 10"6M that had a carbazole was sufficient concentration of to cause 5.5 was 80,000 M efficient was obtained significant 10"5 x exceptionally A quenching in This my parents, The best teachers I work Gary and Carolyn ever and gave me is dedicated to had kissed every Conrow me goodnight spare moment of Thank You every their time night Acknowledgements Many people have put in countless hours support to help me reach Stevenson You introduced -Mr seeds me I goals and aspirations my me to lot and given me a like to thank: would Chemistry in that grew into a love for photochemistry Thanks for of guidance and 10th grade and planted the You inspired your example to become a high school chemistry teacher faculty at SUNY Geneseo -The points of chemistry in my four Geiger Of -Dave from you I interacted Allston, with and it for your and joy ready me realize teaching or as a at RIT in at RIT: Pranita, I also that learned and story Conrow Thank chemical principles advisor: none were as advice, and The assistant large Morrill, and and all people I the professors worked with ways Dr Worman I thank all made sure Julie filled the and each that my very best research so much met such great friends at years of constant our days, for reminding Dr Langner Of at me friendship up over when with Yanira were the RIT with me from all me how I day one cannot RIT chemistry from 7:30 and never really getting too unimportant am - deep into chemistry really is the hands that have helped me shape these instrumental as yours Your patience, lifted and together at school and off campus During two you lab or conversation Rohini D'Souza You two have been happy I am to have encouragement to the all the members of Chemistry office, small and Subu, 5:30 pm, I loved coming home, sharing -My go out Ahmad, Akshy, Anvar, Wei, Dana, Sangita, Xuan, -Elizabeth pages, Greene following pages to the very last We have done how Thanks Dr Kotlarchyk, Dr with a welcome -Chris overstate of discussing research results advice, suggestions, and help You friends -My always the onto laughter through the assistants in the in class, -My committee: made lab a day enriched my experience member (and many late nights) in the halls Chemistry Department at RIT the stockroom, Tom every foundation in the finer that college professors can be great friends -The whom gave me a solid my professors, you, in particular, helped all chemistry is best learned in years You research struggled the last two years in your insight, I thank you your continued for your direction, Table of Contents Abstract i Acknowledgements iii List of Tables v List of Figures viii Introduction 1 Fundamentals of Emulsion Polymerizations 1 Fundamentals of Micelles 1.3 Fundamentals of Photochemistry 10 of Fluorescence 12 Fundamentals 1.5 Classic Models Mechanisms of of Fluorescence Quenching Quenching Quenching Models: 15 18 1.7 Deviations from Classical Quenching in Heterogeneous Media Quenching of 9-Ethylcarbazole by 4-Iodotoluene Derivatives 20 1.8 Fluorescence 25 Experimental 28 Results & Discussion 40 3.1 Preliminary Photophysical Results of Fluorophore & Quencher 3.2 3.3 Quenching Quenching with 3.4 40 in Solution 51 9-Ethylcarbazole in SDS Solutions 61 4-Iodotoluene Quenching 9-Ethylcarbazole with Latex Bound Quencher: P(S-co-NIPMI) 3.5 Quenching P(S-co-VnCz) Latex with 4-Iodotoluene 3.6 Quenching P(MMA-co-VnCz) Latex with 4-Iodotoluene 3.7 Quenching P(MMA-co-VnCz) Polymer with 4-Iodotoluene in THF 3.8 Comparing Quenching Efficiencies 68 73 76 80 Across Matrices 3.9 Thin Films from Latexes 82 85 Conclusion 87 References 89 IV List of Tables Table 1.1 Quenching Mechanisms Table 3.1 Intensity of 9-Ethylcarbazole Fluorescence from Table 3.2 x 10"7Mto Absorption and 10"2 x and 18 Interaction Distances 41 M Solutions in Hexanes Fluorescence Data for 9-Ethylcarbazole in Three Solvents Table 3.3 Table 3.4 Effect of Nitrogen 9-Ethylcarbazole Raw Data from 9-Ethylcarbazole Table 3.7 Raw Data from Raw Data from and Final Results from 9-Ethylcarbazole Table 3.13 Raw Data from 9-Ethylcarbazole Table 3.15 Raw Data from 57 Quenching Experiments of 57 of 57 4-Iodotoluene in Hexanes of 4-Iodotoluene in Toluene Quenching Experiments 58 of 9- 4-Iodotoluene in Toluene Quenching Experiments and and Final Results from 53 4-Iodotoluene in Hexanes 4-Iodotoluene in 0.0091 M SDS Final Results from 64 of 9-Ethylcarbazole and 4-Iodotoluene in 0.0144 M SDS Table 3.16 63 of 4-Iodotoluene in 0.009 M SDS Quenching Experiments 59 of Quenching Experiments and 58 of 4-Iodotoluene in Toluene Quenching Experiments 9-Ethylcarbazole Table 3.14 and of of Quenching Experiments and 52 4-Iodotoluene in Hexanes Intermediate Results from Ethylcarbazole Table 3.12 and of 4-Iodotoluene in 2-Propanol Quenching Experiments 9-Ethylcarbazole Table 3.11 and Final Results from 9-Ethylcarbazole Table 3.10 Quenching Experiments Quenching Experiments and 51 4-Iodotoluene in 2-Propanol Intermediate Results from 9-Ethylcarbazole Table 3.9 and of 4-Iodotoluene in 2-Propanol Quenching Experiments 9-Ethylcarbazole Table 3.8 and Final Results from Intensity of 47 Intermediate Results from 9-Ethylcarbazole Table 3.6 the Fluorescence Quenching Experiments 9-Ethylcarbazole Table 3.5 Purging on 46 Quenching Experiments 64 of 9-Ethylcarbazole and 4-Iodotoluene in 0.0144 M SDS 64 Table 3.17 Raw Data from Quenching Experiments 9-Ethylcarbazole Table 3.18 Final Results from 9-Ethylcarbazole Table 3.19 Raw Data from Raw Data from Table 3.23 Raw Data from Raw Data from Raw Data from Raw Data from Final results Final results Final results in 0.0103 M SDS P(S-co-NIPMI) 70 of P(S-co-NIPMI) P(S-co-NIPMI) P(S-co-NIPMI) in 0.0281 M SDS 73 of 4-Iodotoluene in 0.0087 M SDS 73 of 4-Iodotoluene in 0.0149 M SDS 74 of 4-Iodotoluene in 0.0149 M SDS 74 of 4-Iodotoluene in 0.0204 M SDS 74 of 4-Iodotoluene in 0.0204 M SDS VI 71 of 4-Iodotoluene in 0.0087 M SDS Quenching Experiments and 71 of P(S-co-MPMI) in 0.0281 M SDS Quenching Experiments and 70 of Quenching Experiments and 70 of P(S-co-NIPMI) in 0.0171 M SDS Quenching Experiments 70 of in 0.0171 M SDS Quenching Experiments and of in 0.0103 M SDS Quenching Experiments from P(S-co-VnCz) 69 Quenching Experiments and and Raw Data from P(S-co-VnCz) Table 3.34 and from P(S-co-VnCz) Table 3.33 69 M SDS Quenching Experiments and Raw Data from P(S-co-VnCz) Table 3.32 in 0.0091 M SDS Quenching Experiments and from P(S-co-VnCz) Table 3.31 and Final Results from P(S-co-VnCz) Table 3.30 65 of Quenching Experiments and Final Results from 9-Ethylcarbazole Table 3.29 P(S-co-NIPMI) Quenching Experiments 9-Ethylcarbazole Table 3.28 and Final Results from 9-Ethylcarbazole Table 3.27 and 65 of 4-Iodotoluene in 0.0278 M SDS Quenching Experiments 9-Ethylcarbazole Table 3.26 4-Iodotoluene in 0.0278 M SDS Quenching Experiments of 9-Ethylcarbazole and P(S-co-NIPMI) in 0.0091 9-Ethylcarbazole Table 3.25 of Quenching Experiments and 65 Final Results from 9-Ethylcarbazole Table 3.24 and 65 of 4-Iodotoluene in 0.0213 M SDS Quenching Experiments 9-Ethylcarbazole Table 3.22 Quenching Experiments and Final Results from 9-Ethylcarbazole Table 3.21 4-Iodotoluene in 0.0213 M SDS Quenching Experiments 9-Ethylcarbazole Table 3.20 and of 74 Table 3.35 Raw Data from P(S-co-VnCz) Table 3.36 Final Quenching Experiments and from results 4-Iodotoluene in 0.0263 M SDS Table 3.38 Table 3.39 Table 3.40 Table 3.41 Table 3.42 Table 3.43 in 0.0263 M SDS 75 Results from Quenching Experiments of P(MMA-co-VnCz) and 4-Iodotoluene in 0.008 M SDS 77 0.0141 M SDS 77 Results from Quenching Experiments of P(MMA-co-VnCz) and 4-Iodotoluene in Results from Quenching Experiments of P(MMA-co-VnCz) and 4-Iodotoluene in 0.0164 M SDS 77 0.0199 M SDS 77 0.0257 M SDS 78 Results from Quenching Experiments of P(MMA-co-VnCz) and 4-Iodotoluene in Results from Quenching Experiments of P(MMA-co-VnCz) and 4-Iodotoluene in Raw Data from Quenching Experiments of P(MMA-co-VnCz) Copolymer and 4-Iodotoluene Final Results from P(MMA-co- Table 3.44 75 Quenching Experiments of P(S-co-VnCz) and 4-Iodotoluene Table 3.37 of VnCz) in THF 80 4-Iodotoluene in THF 81 Quenching Experiments Copolymer and Quench Data from Each Matrix VII of 84 10"* 5.07 x 6.28 x Table 3.35 Raw Data: 10* 392.10 403.13 2.019 399.17 401.52 2.027 P(S-co-VnCz) Quenched by 4-Iodotoluene in 0.02634 Total Percent Total Absorbance Absorbance @ 295 nm Absorbed by 9-EtCz Absorbance Of Ouencher Solution [4-iodotoluenel (Molarity) 0.7461 100.00% 0.9157 0.7616 97.96% 0.9450 0.0293 0.7509 99.36% 0.9451 0.0294 0.7681 97.14% 0.9707 0.0550 0.7757 96.18% 0.9918 0.0761 0.7715 96.71% 1.0041 0.0884 0.7777 95.94% 1.0222 0.1065 0.7909 94.34% 1.0506 0.1349 0.7767 96.06% 1.1179 0.2022 10 6.5 x 7.4 x 10 1.4x10* 1.9 x 2.2 x 2.7 x 3.4 x 5.0 x 10* 10"* 10"4 10* 104 Table 3.36 Final Results: @ 282 P(S-co-VnCz) Quenched by 4-Iodotoluene Nominal @ 282 nm in 0.02634 M SDS Corrected r4-iodotoluenel (Molarity) Fluorescence 834.06 834.06 1.000 668.02 681.90 1.223 603.94 607.83 1.372 574.42 591.36 1.410 538.36 559.72 1.490 7.35 x 7.38 x 10 1.38x10* 1.91 x 2.22 x 2.67 x 3.38 x 5.07 x result of access model of 368 10 10* 10"* 10"* 10"* 10* the quenching that of SDS and micelle downward curvature, somewhat access effect upward linear low equaling the curving is concentrations above 1.542 512.45 1.628 469.89 498.10 1.674 370.96 386.17 2.160 x two quenched regime molarity 10"4M The consequence of styrene-carbazole The efficiency interactions In 75 to be a had plot appeared to but this may be due to the hindered access model irregularity a quencher continued The Stern-Volmer joint Stern-Volmer The hindered fit the hindered the Stern-Volmer plot SDS concentrations, by 4-iodotoluene for the fluorophore: regimes however, effects of a nm 541.03 concentration, the Io/I 368 nm) 523.22 inaccessible quencher expected (368 491.63 predicts regardless of at Fluorescence nm P(S-co-VnCz) latex accessible regime and a quencher function nm Solution The be M SDS Nominal of and Perrin model, dominates the plots in addition at where 4-iodotoluene Figure 3.26 is a to the heavy-atom quenching of 4-iodotoluene, The effect of exciplex the exciplex is not concentration and 4.0 formation becomes 4-iodotoluene a consideration within the latex particle fully understood in the context of increasing the micelle concentration -i ? 0.0087M SDS 0.0149MSDS 3.5 - * A0.0204MSDS 0.0263MSDS 3.0 - ^-^p> %2.5 2.0 - y - "^^ yV^s*^.,^* 1.5 ""^ s^-^Z? - n i 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006 0.0007 0.0008 [4-iodotoluene] Figure 3.21 Stern-Volmer Plots: 3.6 P(S-co-VnCz) Latex Quenched by 4-Iodotoluene in SDS Solutions Quenching P(MMA-co-VnCz) latex with 4-iodotoluene The quenching concentration The concentration range maximum concentration of (0.86 significant concentration 4-iodotoluene volumetric P(MMA-co-VnCz) latex of 10"6 x data from any were estimated flasks M to 4.3 based on 10"5 x was extremely x M) to extract any were the dilutions 76 10"5 to quencher 4-iodotoluene (4.3 too small absorption wavelength and pipettes sensitive carried out M) and Concentrations in the lab the of with standard Again, equation using latex with no nitrogen purge was 23 rather than 4-iodotoluene Table 3.37 Raw Data: 25 The P(MMA-co-VnCz) in Tables 3.37 - 3.41 781.77 1.000 454.89 1.719 0.719 1.72x10 x 10 2.15 x 2.58 x 3.45 x 4.31 x Table 3.38 Raw Data: 10 10 10 P(MMA-co-VnCz) Estimated [4-iodotoluenel 6.88 10 x 1.38x10 1.72x10 10 2.06 x 2.75 x 3.44 x 10 10 [4-iodotoluenel 10 6.88 x 1.38 x nm lndo/1) 363 nm 2.238 1.238 314.47 2.486 1.486 283.71 2.756 1.756 244.02 3.204 2.204 224.97 3.475 2.475 Latex Quenched Fluorescence 363 Io/I 363 349.30 nm by 4-Iodotoluene in 0.0141 M SDS Io/I 363 ln(Io/I) 363 nm nm 781.36 1.000 578.41 1.323 0.323 487.91 1.568 0.568 455.43 1.680 0.680 438.59 1.744 0.744 400.51 1.910 0.910 363.50 2.105 1.105 Table 3.39 Raw Data: P(MMA-co-VnCz) Latex Quenched Fluorescence Estimated 363 nm by 4-Iodotoluene in 0.0199 M SDS Io/I 363 nm ln(Io/I) 363 nm 806.51 1.000 640.27 1.260 0.260 10 566.80 1.423 0.423 1.72x10 532.08 1.516 0.516 10 511.84 1.576 0.576 10 473.82 1.702 0.702 10 426.65 1.890 0.890 2.06 x 2.75 x 3.44 x Table 3.40 Raw Data: P(MMA-co-VnCz) Latex Quenched Estimated Solution r4-iodotoluenel quenching in P(MMA-co-VnCz) Latex Quenched by 4-Iodotoluene in 0.0081 M SDS 10'6 determined 8.62 Solution ratios were Fluorescence 363 nm Stern-Volmer [4-iodotoluenel Solution and results of the matrix are given Estimated Solution necessary Fluorescence 363 nm by 4-Iodotoluene in 0.0257 Io/I 363 nm M SDS ln(Io/I) 363 nm 789.54 1.000 10" 683.63 1.155 0.155 1.38x10 596.74 1.323 0.323 10 537.95 1.468 0.468 10 513.87 1.536 0.536 10 468.84 1.684 0.684 6.88 x 2.06 x 2.75 x 3.44 x 77 Table 3.41 Raw Data: P(MMA-co-VnCz) Estimated Solution Latex Quenched by 4-Iodotoluene in 0.0164 M SDS ln(Io/I) Io/I Fluorescence [4-iodotoluenel 363 10"" 8.62 x 1.72 x 2.58 x 3.45 x 4.31 x 8.62 x 1.29 10 10 2.15 363 nm nm 779.51 1.000 0.000 563.64 1.383 0.383 474.69 1.642 0.642 421.34 1.850 0.850 371.49 2.098 1.098 340.63 2.288 1.288 243.57 3.200 2.200 209.59 3.719 2.719 189.68 4.110 3.110 184.23 4.231 3.231 10 10 10 10 xlO4 1.72x10* 363 nm 10* x Although the fluorescence quenching of P(MMA-co-VnCz) was extremely 10" low 4-iodotoluene concentrations, efficient at M, downward curvature quencher was extended clear was observed beyond (see Figure 3.22) As the 10"4 x at quencher concentrations above M for a solution of that a saturation point of quenching was reached was unable dispersed to interact particles The latex fits the hindered 3.5 with sections of inability of the the quencher SDS, it became (see Figure 3.23) The to interact x concentration of 0.0164 M latex, presumably in the inner core quencher of these with specific regions of the access model of quenching ? 0.0080MSDS A 0.0141 M SDS 3.0 ? 0.01 99M SDS 0.0257M SDS 0.00E+00 5.00E-06 1.00E-05 2.00E-05 1.50E-05 2.50E-05 3.00E-05 3.50E-05 [4-iodotoluene] Figure 3.22 Stern-Volmer plots of P(MMA-co-VnCz) Latex Quenched 78 by 4-Iodotoluene in SDS Solutions 5x" y + = -2E+1 9E+1 2E+08X2 x3 + - R2 = 38871 x + 0.9993 Linear (363 nm) Poly (363 nm) O.OOE+00 5.00E-05 2.00E-04 1.50E-04 1.00E-04 [4-iodotoluene] Figure 3.23 Stern-Volmer There the P(MMA-co-VnCz) Quenched by 4-Iiodotoluene in 0.0164 was a clear effect of latex (see Figure 3.24) The was the plot of less drastic than the trapping was the latex the latex out of probability that a quencher would latex However, trapped The once a quencher effect of in the the latex the change permanent migration of quencher be in held slope micellar matrix particles concentration was concentration, and therefore an increase the quenching efficiency in the Stern-Volmer change faster than diffusion increased, concentration on change observed of quencher within micelles was SDS Diffusion particles constant micelle, diffused from in SDS unable a micelle in this latex This out of 79 phase the be within matrix attributed to uncrowded concentration The increase in SDS an increase in the to interact into a with the fluorescing latex particle, it became concentration was muted into the latex can As the SDS in micelles, did lead to a M SDS by the semi 80000 70000 60000 y - = 719.42x R2 = g_ 50000 -0.9468 0.9903 o 55 40000 y> 30000 20000 10000 0.008 0.01 0.012 0.014 0.016 0.018 0.028 0.026 0.024 0.022 0.02 [SDS] Figure 3.24 Stern-Volmer Slopes from P(MMA-co-VnCz) Quenched by 4-Iodotoluene as SDS Molarity 3.7 Quenching P(MMA-co-VnCz) polymer extracted from a The fluorescence quenching matrix A (THF) The dissolved (Tables 3.42 9-ethylcarbazole alkylcarbazole 349 P(MMA-co-VnCz) solid copolymer was extracted tetrahydrofuran analysis of 3.43) quenched in the 363 nm and and nm from the latex was carried out copolymer was estimated and from the in the with and the same way 2-propanol The Function beyond the latex solid was dissolved in by 4-iodotoluene as of 4-iodotoluene was extended copolymer was quenched by 4-iodotoluene in (0.94:1) latex a and the the analysis of concentration of from the fluorescence the peak ratio at experimental mole percent of vinylcarbazole per mass of copolymer Table 3.42 Raw Data: P(MMA-co-VnCz) Quenched Total Nominal [4-iodotoluenel Absorbance @ 294 by 4-Iodotoluene in THF Percent Absorbance Absorbed by Of Ouencher 9-EtCz nm @ 294 nm Fluorescence 363 nm Solution (Molarity) 1.0735 100.00% 783.30 0.00161 1.2197 88.01% 0.1462 612.26 0.00312 1.3574 79.08% 0.2839 494.57 0.00385 1.4231 75.43% 0.3496 445.89 0.00543 1.5671 68.50% 0.4936 372.30 0.00647 1.6613 64.62% 0.5878 353.69 0.00868 1.8615 57.67% 0.7880 266.56 J 80 j Table 3.43 Final Results: P(MMA-co -VnCz) Quenched by 4-Iodotoluene in THF Calculated Corrected r4-iodotoluenel (Molarity) Fluorescence Solution 783.30 1.000 0.00161 695.64 1.126 0.119 0.00312 625.36 1.253 0.225 0.00385 591.10 1.325 0.282 0.00543 543.48 1.441 0.366 0.00647 547.35 1.431 0.358 0.00868 462.22 1.695 0.527 The solution was a Perrin rigid model matrix quenching (see Figures 3.25 that is characteristic from the Perrin plot, 61.7, translates into (using equation distances, ln(Io/I) Io/I 368 nm) 368 nm 7) This radius is in line which act on the order of ~4 with of a and 3.26) The an effective typical quenching heavy-atom + = = 0.003 of interaction 0.004 0.005 0.006 52.154x+1 0.9993 0.007 0.008 [4-iodotoluene] Figure 3.25 Stern-Volmer Plot 2.90 A A R2 0.002 radius of quencher 3335.7x' 0.001 copolymer typical Perrin environment The y nm by 4-iodotoluene results of carbazole within a copolymer solution quenched exhibited typical slope (368 P(MMA-co-VnCz) Quenched by 4-Iodotoluene in THF 0.009 0.6 0.5 0.4 y 0.3 R2 = c 0.2 = 61 748x 0.9948; 363 nm - 0.1 0.0 m-1 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 [4-iodotoluene] Figure 3.26 Perrin Plot 3.8 of P(MMA-co-VnCz) Comparing Quenching Efficiencies Across Matrices From the 3.44) it is clear results of fluorescence quenching in calculated at slopes low quencher for the 3.18 3.24) Quenching in is nearly three times the efficiency of a S-V factor in diffusivity matrices where slopes versus more efficient column reflect the is SDS effected Stern-Volmer Stern-Volmer P(MMA-co-VnCz) single-phase media difference in formation is in the third micelle matrix and respective plots of mirrors results concentrations, from the and the various matrices (see table that the matrix affects the interaction between alkylcarbazole species and iodotoluene derivatives The S-V Quenched by 4-Iodotoluene in THF latex linear The solution were extrapolated concentration at by plot was slopes 0.01 M SDS (Figures solvent viscosity The quenching in hexanes than in 2-propanol This efficiency of that the quencher contain in the two solvents toluene and polystyrene Exciplex The quenching 4-iodotoluene in toluene is noticeably lower than in 2-propanol 82 4-iodotoluene the quenches the fluorescence of fluorescence of P(MMA-co-VnCz) The reduces the effect of the iodotoluene exciplex acts as a high local In the P(MMA-co-VnCz) efficiency is nearly 1,000 fold quenching sensitivity quenching low in fluorophore quenched greater than the be used to latex design particles The and a greater toward the migration quenching by 4-iodotoluene, non- leads to a sensitivity the global quenching quenching in 2-propanol This increase in 'amplified' fluorescence a number of probes or sensors to measure concentrations of organic molecules that are too single-phase aqueous systems The matrix could and quencher migrate of either micelles or concentration of quencher and extreme case, quencher that competing quencher In multi-phase matrices, the fluorophore polar, non-continuous phase times less efficiently than P(S-co-VnCz) ten upward curvature of Stern-Volmer indicates that there is both non-viscous environments consequence of the analytes that there is saturation of dynamic The efficiency diffusing into concentrations of quencher and The a are greater efficient not able latex reasonable core to assume More likely, the core of SDS, and is a the local phase indicate the latex particle random copolymer coil within outer shell of Extending this latex is the model that 9-ethylcarbazole some of 83 where in in alkylcarbazole copolymers to diffuse into this around component than in the bulk fluorophore trapped in the in the P(MMA-co-VnCz) latex P(S-co-NIPMI) latex, it is through the entire for the solution and micelle much greater the dispersed phase, the latex The quenching that does take place extremely quenching quenching is the quenching curves Furthermore, 4-iodotoluene is in the hexanes and static of fluorophore a significant portion of plots to the does not diffuse the polymer-bound quencher was kept from interacting with 9-ethylcarbazole, which resides in dispersed phase In this case, the effective, considerably lower than quenching NIPMI) was the more polar regions of the accessible quencher concentration the concentration within the latex particle Perrin model rather than saturation observed, quenching because the on the outer shell was sufficient to quench the fluorescence Quenching the extracted P(MMA-co-VnCz) polymer in purely static solution and within the in nature A Perrin type quenching this may serve as a feasible P(MMA-co-VnCz) latex quenching makes model mechanism for the type In both cases, the coil, though in the THF solution there saturation is of a make a most viscous P(S-co- 9-ethylcarbazole of THF solution was expected for polymer is oriented Matrix Type of definitive case, but the type likely static Ouenching Mixed S-V & Perrin; Downward curving Perrin in 2-propanol 9-EtCz & 4-iodotol Mixed S-V & Perrin; In hexanes Upward curving Perrin 9-EtCz & 4-iodotol Mixed S-V & Perrin; In toluene Upward curving Perrin Mixed S-V & 9-EtCz & 4-iodotol in 0.01 M SDS in nature S-V Slope 61.5 178 22.7 Perrin; Upward curving S-V 4084 Perrin 6655 9-EtCz & with (pure static) 0.01 M SDS P(S-co-VnCz) latex & 4- iodotol in 0.01 M SDS Hindered Access; Curving S-V 5457 Hindered Access; Curving S-V 56310 Downward P(MMA-co-VnCz) latex & 4-iodotol in 0.01 M SDS Downward P(MMA-co-VnCz) solution & 4-iodotol in THF Perrin (pure static) 84 in occurs a random interactions The Table 3.44 Quench Data from Each Matrix 9-EtCz & 4-iodotol a polymer quenching that are more solvent-polymer it difficult to quenching in the fluorescent latexes is P(S-co-NIPMI) latex may be 66.4 of 3.9 Thin Films from Latexes Thin films Films were studied spectra of the from the constructed of both P(S-co-VnCz) copolymers, in Figure that of typical carbazole latexes copolymer and 3.27, have because the concentration of alkylcarbazole comparison of concentrations The three peaks peaks are a result of place Internal The The excited triplet from nm and S s + between the an excited such as film relative There high, to the each copolymer nm and the and 360 nm.) These alkylcarbazole, ' A*, A, overlaps state of an alkyl carbazole alkylcarbazole A resulting in : 3A* S -> A -^ + neither behavior Phosphorescence is Also, (the the concentration of S + hc/X the latex solution more intense in fluorophore within the other matrices was no serious attempt make a series of the new peaks formed, intersystem crossing in the thin film matrix, but thin films rigid environments, is to the triplet styrene and A -* peaks are not seen the alkylcarbazole, an exciplex to range nm are phosphorescent peaks 3S* S -+ in triplet state of the alkylcarbazole nor redissolved polymer exhibited such was quite 520 of styrene relaxes phosphorescence was observed difficult to After lA* A* same the peak ratios at 345 excited singlet state of styrene, conversion occurs phosphorescence The of on These three not explain is nearly the in The the familiar styrene tail at 320 formation between styrene, S, the exciplex the excited triplet state takes is based between 460 components of the polymer nm Re-absorption does spectrum were prepared peaks and peak ratios similar fluorescence P(S-co-VnCz) has P(MMA-co-VnCz) the final matrices that P(MMA-co-VnCz) nm, in addition to peaks at 460 nm, 500 nm, and 520 in the were three or to study quenching more films that had 85 within these matrices It was reproducible fluorescence intensities With the variation in fluorescence intensities fluorophore precisely calculate results of quenching in and without a reliable method or quencher concentration, it is difficult to interpret the thin films 1000 P(S-co-VnCz) 900 P(MMA-co-VnCz) 800 320 370 420 470 520 Wavelength Figure 3.27 Fluorescence Spectra of P(S-co-VnCz) and 86 570 (nm) P(MMA-co-VnCz) Films 620 to Conclusion The fluorescence quenching 4-iodotoluene, and its quenching, and hindered the matrices studied magnitude greater than Stern-Volmer and sensitive quenching latexes in the bulk slopes and was concentrations on the order of 9-Ethylcarbazole quenching exciplexes with exciplex formation interactions obstacle, but the studies, exciplex side-reactions of toluene in formation in any delivery solvent, in one of to create isolated regions In the led to a wide P(MMA-co-VnCz) latex to changes in 4-iodotoluene as a delivery 9-ethylcarbazole drawback to using were information for within adds an unneeded easily an alkylcarbazole it was is that it readily the quenching synthesize its be involved in any polymer analog limitation Even with maximum concentration was 87 Although of complexity aqueous solutions was a micellar solutions of simpler that did not appear to easy to synthesized possible studies on copolymer the scope layer aqueous solvent countered solution and styrene within a copolymer interactions, matrix and 2-propanol of was a stable quencher this analyte, in least at and quencher were orders of efficiencies use of provides a wealth of 4-Iodotoluene solubility greatest or solvent-analyte in fluorophore Its low solubility in this shortcoming Copolymer latex analogs forms by dynamic creation of such regions sensitive analogs, 10"6M was a sufficient from 9-vinylcarbazole The copolymer were each observed fluorophore The its mixed static and were employed solution extremely and to the matrix surrounding the quenching, the concentration of specifically, the quenching solutions was a minor exciplex access model Micelles within a solution where range of 9-ethylcarbazole, derivatives, is highly Purely static quenching, analytes of The the aid of a limited to 10" M The x can concentration of quencher within a be increased Latex further study by changing the monomer ratios solutions will provide a Quenching in Quenching between One could containing Further design design work could also use useful to in the and contain more particle the the other than hand, synthesis hopefully rewarding particles one copolymer also prove may that contains a core copolymer amplified on that quenching system is for possible insightful fluorophore is labeled quencher observed in latexes to probes and sensors and polymer solutions polymer solutions in the latex by a second shell be done to fluorescent progression of matrices becomes type of latex copolymer surrounded Films to latexes that two oppositely charged latex a single a number of challenging latex copolymer, may be another area of naturally flows from polymer future interest The single-phase solutions films The information that is analysis of prior and subsequent studies to micelles obtained from to latexes each matrix References Lehrer, S Biochemistry 1971, 10, 1971 Eftink, M.; Ghiron, C Biochemistry 1976, 15, 672 Elaissaui, A.; Chauvet, J P.; Halle, M A.; Decavallas, O.; Pichot, C; Cros, Ph J Colloid Interface Sci 1998,202,251 Charreyre, M.; Tcherkasskaya, O.; Winnik, M Langmuir 1997, 13, 3103 Wong, J E.; Duchsherer, T M.; Pietrau, G.; Cramb, D T Langmuir 1999, 15, 6181 Matzinger, S.; Hussey, D.; Fayer, M D J Phys Chem B 1998, 102, 7216 ? 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