This action might not be possible to undo. Are you sure you want to continue?
Bull. Korean Chem. Soc. 2010, Vol. 31, No. 6 1753 DOI 10.5012/bkcs.2010.31.6.1753
Imsung Yoo, Bora Yoon,† and Simon Song* Department of Mechanical Engineering, Hanyang University, Seoul 133-791, Korea. *E-mail: firstname.lastname@example.org † Department of Chemical Engineering, Hanyang University, Seoul 133-791, Korea Received March 23, 2010, Accepted May 3, 2010 Key Words: Polydiacetylene, Temperature, Microfluidic chip, Fluorescence Since the pioneering discovery by Wegner,1 polydiacetylene (PDA), a family of conjugated polymer, has been extensively 2-10 investigated in the field of sensors. Owing to the unique selfassembled state and the poly(ene-yne) backbone structure, the conjugated polymer displays a phase transition upon environmental perturbations, and this results in a brilliant blue-to-red color change in most cases. Unlike other conjugated polymers which require tedious multistep modification processes, PDA can be readily prepared from diacetylene supramolecules in an aqueous-friendly environment by UV irradiation (Scheme 1). In addition, amphiphilic nature of the diacetylene monomer allows fabrication of various nanostructures including nanotubes, nanowires, nanovesicles, nanohelices, and nanoribbons. The apparent blue-to-red color transition of PDA has served as a foundation for the construction of many colorimetric chemosensors for the detection of target molecules of interest such as DNAs, proteins, ions, and volatile organic compounds 2-10 (VOCs). PDA has been also used as a probe molecule for 11 the monitoring of temperature. Another attractive feature of PDA that has been neglected for a long time is its nonfluorescence-to-fluorescence transition upon stimulation.12-13 In fact, PDA emits red fluorescence when it undergoes a blue-to-red phase transition. Recently, the stimulus-induced fluorogenic change of PDAs has begun to re6,14,15 ceive substantial attention as an alternative sensing signal. In addition, the fluorogenic property of PDA allows fabrication of microarrayed and microfluidic PDA sensor systems, which are almost impossible to obtain by using the conventional 9 colorimetric method. We reported that temperature in a microfluidic channel could be monitored using the thermofluorescent PDA supramole11 cules. Microfluidic systems have been emerged as powerful tools due to its several advantages such as relatively short diffusion distance, nascent consumption of samples and reagents, large interfacial areas and the capability of continuous analysis. These salient properties enable the microfluidic systems as good
R1 R2 R2 R2 R1 R1 R1 R2 R1 R2 R1 R2
16-18 Howalternatives to the conventional batch-type systems. ever, temperature control or monitoring is an important issue in many applications of microfluidic systems. For example, active temperature control or monitoring is often necessary when performing enzyme-activated reactions, chemical reactions or PCR 19-22 Thus, a for DNA amplification on a microfluidic chip. 22 couple of methods using Rhodamine B or thin film thermo23-25 have been developed to measure temperature on a couples microfluidic chip. We also reported that PDA can be used as a temperature sensor in the range of 40 ~ 60 oC using its linear relationship between temperature and its fluorescence inten11 sity. It would be more desirable, however, if PDA-based temperature sensor could be utilized in a wider temperature range. As part of our continuing efforts to the development of PDAbased sensor materials, we now report PDA-based temperature sensors derived from different diacetylene monomers for the temperature measurements of a microfluidic channel in different temperature ranges. Temperature sensor chips and the experimental setup are 11 similar to that used in our previous work. In short, a chip consists of a polydimethylsiloxane (PDMS) substrate bonded to a glass slide and has three inlets and one outlet as illustrated in Figure 1. A blue phase, nonfluorescent PDA solution is injected to the center inlet and corn-oil to two sheath inlets with syringe pumps. PDA droplets are generated by hydrodynamic instability 26 at the inlet junction. While the droplets flow in the main channel, they are subject to a constant heat flux from a microheater integrated on the glass slide. The microheater made of ITO thin film generates Joule heating, resulting in linear temperature
PDMS Channel Oil Blue PDA Oil DC Power supply ITO microheater
Pad Temp Inlet Temp Outlet Temp
Thin Film Thermocouple DAQ board
Scheme 1. Formation of PDA from self-assembled diacetylene monomers
Figure 1. Schematic of the PDA temperature sensor microfluidic chip.
Thus. Thermally stimulated PDA droplets after turning on the heater are shown in Figure 3B and 3C. PCDA-EDA and PCDA-AEE. 1-Ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC) was purchased from Tokyo Chemical Industry. Droplets generated at the junction of inlet channels march along the microchannel stably and regularly.5 C 36 C 39 . 6 O O OH OH Notes (A) 19 C 22. and emitted red fluorescence upon the stimulus. PCDA-AEE was synthesized following modified 29 procedure described in the literature. Finally. Images of PDA derived from PCDA-EDA or PCDA are omitted for simplicity. distribution along the channel. and PCDA-AEE has a linear range of 33 to o 46 C.3 C 26 C 29 C 32. PDAs derived from three different diacetylene monomers. PCDA-EDA resulted in the lowest range o from 23 to 34 C. current study addresses that precise temperature monitoring is possible by choosing proper diacetylene monomers. Images of PDA droplets. C) heat treatment. In addition. In conclusion.12-pentacosadiynoic acid (PCDA) and EDA.1754 Bull. N-Hydroxysuccinimide (NHS) and 2-(2-aminoethoxy)ethanol (AEE) were purchased from Aldrich. we integrated T type thin-film thermocouples at the entrance and exit of the main channel to measure the temperature distribution along the channel so that we can compare the fluorescence intensity of PDA droplets with the temperature. 0 50 60 Temperature ( C) Figure 4. derived from PCDA-AEE. are taken 35 mm downstream of the inlet junction. Soc.12-Pentacosadiynoic acid (PCDA) was purchased from GFS Chemicals. The highest temperature range obtained with PCDA-derived PDA is presumably due to the strong headgroup interaction among carboxylic groups in the polymerized supramolecules. Among various diacetylene monomers investigated. PCDA-EDA. was prepared from activated 10.5 C 53 C 56 C o o o o o o o o o o o o PCDA PCDA O O N N H H NH2 NH2 PCDA-EDA PCDA-EDA O O (B) 120 PCDA-AEE PCDA-AEE N N H H O O OH OH 100 Figure 2. PCDA.3 C 43 C 46 C 49. The ethylenediamine (EDA)-derived diacetylene monomer. The vertical brown lines are the ITO microheater. Optical (A and B) and fluorescence (C) microscopic images of PDA droplets (PCDA-EDA) in the middle of the main channel before (A) and after (B. Similarly. Olympus). 0. the PCDA-AEE was obtained by coupling activated PCDA and aminoethoxyethanol (AEE). PCDA-EDA and PCDA-AEE. It is clear that they experienced visible color transition from blue to red. PCDA-EDA was prepared according to the known 28 procedures. Figure 3A displays an optical image of blue-phase PDA sensor droplets in the middle of the main channel at room temperature (20 oC). It is evident that each PDA has a different temperature range where the relation is linear. PCDA has the highest temperature range from 41 to 53 oC.) 80 60 (A) PDA droplets (B) (C) 40 Microheater Thermally stressed PDA droplets 20 PCDA-AEE PCDA-EDA PCDA 20 30 40 o Figure 3. PDAs derived from three monomers shown in Figure 2 were found to be most efficient in terms of temperature monitoring in the microfluidic device. 2010.67 mmol) of 10. the results described above demonstrate that temperature monitoring in a microfluidic channel is possible with PDA supramolecules. and PCDA-AEE displayed different temperature ranges where the temperature is linearly proportional to the fluorescence intensity of PDA droplets. Fluorescence microscopic images of PDA droplets derived from PCDA-AEE (A) and fluorescence intensity variations of PDA droplets with respect to channel temperature (B). and alcohol) and should allow different colorimetric sensitivities when they are transformed to polymers owing to the different degree of head group interactions. and are displayed in Figure 4A for various channel temperatures.12pentacosadiynoic acid (PCDA). Figure 4B shows the relations of the temperature and the fluorescence intensities of PDA droplets 27 derived from PCDA. Vol. u. These PDA droplets are monitored by using an inverted fluorescence microscope system (IX71. Intensity (a. Structures of diacetylene monomers: PCDA. PCDA-EDA. No. Korean Chem. In addition. Experimental Section Materials. amine. 31.46 g (4 mmol) of N-hydroxy- . 1 g (2. These three monomers have different head group structures (acid. 10. The fluorescence of red-phase PDA droplets becomes stronger with increasing the channel temperature.
. the microheater and thermocouples were electrically insulated by sputtering ONO (SiO2 250 nm.p. 5.21 g (2. Okawa. Ma. Schrader. Molt. Ahn. the wafer is exposed to UV light (Jaesung Corp. 409. 1. Charych.70 mmol) of 2-(2-aminoethoxy)ethanol (AEE) were dissolved in dichloromethane and stirred for 3 h at room temperature.56 mL (25. 4H). Science and Technology(MEST) of Korea (Grant number: K20901000006-09E0100-00610) and the Seoul R& BD Program (10919). S. National Instruments) and LabView software (National Instruments) were used to acquire voltages out of thin film thermocouples. 18. 2008. A diacetylene monomer was dissolved in 2 mL of chloroform. Am. By using this coefficient. 3038. KD Scientific): one for the PDA flow and the other for the oil flows. a thermocouple amplifier (SCXI1102. Yoon. Yoon.. 312. 1H).Notes succinimide (NHS) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) were dissolved in dichloromethane and stirred for 2 h at room temperature. Science 1993. The coefficient correlates the voltage of a thermocouple with the temperature difference between the sensing position and the other end of the thermocouple. T. Vol.88 (t. PDA solutions used in this study were prepared as follows. A. A. D. Gill. 38. Chae.85 (t. 10000.98 g (83%) of the desired product. Then. 154. Kim. 3. Using the lift-off process. 261. J.57 mmol) of PCDA-NHS. Chem. and SiO2 250 nm) of 800 nm in thickness on the wafer (Daeki Hi-Tech). 2H).. 1. K. the residue was dissolved in ethyl acetate and washed with water.57 (32H). 9.06 (t. 1.. The flow rates of a PDA solution and an oil flow are maintained at 0. 3H). G. No. Sensor test and temperature measurements.. 42. 2. 3264. 2005.8 µV/K. N. Specak. Ballesteros. PDA preparation. Thin-film thermocouples were calibrated to determine their Seeback coefficient which is known 31 to be different from those of the bulk thermocouple. Nature 2001. and 2. Syringes were connected to the inlets of the microchannels through capillaries and microfluidic fittings (LabSmith). Soc. the residue was dissolved in ethyl acetate and washed with water. 2009. Chem. D. The resulting solution was filtered through a 0. a photoresist (PR) (AZ 4620) is spin-coated for 10 s at 500 rpm and 40 s at 2500 rpm to a uniform thickness of 3 µm on the glass wafer that is intensively cleaned with acetone. Soc. H NMR (300 MHz.p. M. Sorona) on to the wafer to a thickness of 200 nm. B.. Thin-film thermocouples are integrated on the glass wafer by sequentially depositing copper and constantan. The organic solvent was removed by purging with N2 gas to make a thin film inside the vial.24 (t.-M.21g (96%). Cheng. Rev.. Temperature calibration. 585. Angew. Sun. Ulvac) after spin-coating and developing Bull. Fluorescence emitted from thermally stimulated PDA droplets were imaged using an inverted fluorescence microscope (IX71W. 2H).60 (m. Am. 3. the ITO is sputtered (Sputter System. J. G. 683. S. W. J.. 2. R. and is thoroughly cleaned with DI water. Wegner. 31. S.87 (s. Aono. Si3N4 300 nm. 55. H. 2010. As the final process.12 mL/h. PCDA-AEE: m.68. 1030. 2. we were able to measure temperatures at the entrance and exit of the main channel. J. 2H). Bardeen. 1H)... M ller. 6 1755 PR on the wafer by the same method as described beforehand and depositing a 20 nm Ti film by E-beam evaporating (EBX 1000. 7.. Chem. The PDMS substrate contains a microchannel network whereas the glass slide has an ITO film microheater and thin film thermocouples.. Ulvac) for a better adhesion of copper to the glass. Int. After concentration under vacuum. J. 4H). The organic layer was dried over MgSO4 and concentrated under vacuum to give a residue which was subjected to silica gel column chromatography using ethyl acetate/methanol as eluent. It is o soft-baked at 100 C for 4.. J. Ed.24 (t. D.) for 8. Chem. The PDMS substrate is fabricated by using standard soft lithography and molding techniques described in our previous re30 port. 3. We found that the Seeback coefficient is 16. 67 . J.60 (t. The sample was then heated o at 80 C for 15 min and probe-sonicated for 15 min. 5. Nagy. Next. 1972. PR was stripped off to complete the copper patterning.48 (q. 2. 2. Copper lines of a 200 nm thickness were first patterned with E-beam evaporator (EBX1000. Olympus). Acknowledgments. M. 6.57 (32H). Makromol. Then. Chem. C.-M. A. A microfluidic chip is composed of a PDMS substrate bonded to a glass slide. M. First.74 oC. 72 . and deionized (DI) water. yielding 0. M. Polymerization was carried out at room temperature 2 by exposing the solution to 254 nm UV light (1 mW/cm ) until the absorption at 640 nm reaches a maximum (ca. Acc. The organic layer was dried over MgSO4 and concentrated under vacuum to obtain N-hydroxysuccinic ester of PCDA (PCDA-NHS). o 1 PCDA-NHS: m. 2H).02 mL/h and 0.. CDCl3) = 0. Y. I.56-3. 10. isopropyl alcohol (IPA). J.18 (t. . Olympus) with a 4x objective and a color CCD camera (DP70. Adv.. Mater. Chem. 5 min). Res. 41. Kim. 3.88 (t. Only exception is that it was deposited by thermal evaporating (Daeki Hi-Tech) to a height of 400 nm. Soc. 8. PDA solutions and corn oil are inserted to a microfluidic chip by using two syringe pumps (KDS120. CDCl3) = 0. Jelinek. 2. Fabrication processes for the microheater and thermocouples are as follows. Herm.5 min.5 C. 35. yielding 1. 4H). Next. Science 2006. S. Bednarski. J. Kolusheva. Kim. References 1. an ITO film microheater with a width of 50 µm is completed by the lift-off process that strips off PR with acetone. we determined a temperature at an arbitrary 27 position in the channel by interpolating the two temperatures.. O. O. W. 805. constantan lines were patterned with the same procedure as the copper lines with careful alignment (MA6-II. 2007. Lauher. Finally. After concentration under vacuum. Finally.8 µm filter.-M. and deionized water (30 mL) was added to the vial to yield a total monomer concentration of 1 mM.25-1. 1H NMR (300 MHz. Goroff. Q. This research was supported by the International Research & Development Program of the National Research Foundation of Korea (NRF) funded by the Ministry of Education. 2003. 2. 1958.5 min through a film mask with a microheater pattern. J.25-1. 127.76 (q. 3H).. Lee. Korean Chem. Fabrication of microfluidic chip. respectively. 129. 4H). 4. Suss MicroTec).5 min. Soc. v/v) to increase the viscosity.. is developed for 2.. 2006. and the filtrate o was allowed to stand at 4 C for 12 h before being mixed with ethylene glycol (EG) (PCDA : EG = 98 : 2.
73.. 1998. R. I. L. 229. Cremer. Chem. G. Langmuir 2000. Carpick. Locascio. 24... N.. K. 3rd ed.. S. P. Actuators B 2006.. S. M.. K. T.-M. Soc. 58.. D. Mao. Lee. Vol. S. P. J. 1601. Kim. J. Am. 1270. No. Crawford.. W. 21. 31. Kitamori.. Instrum. S... Cygan. S. American Institute of Physics 1993. Chem. Medintz. 2008. J. 28. 64. P. Biochip J. Chem. 64. Tokeshi. Mathies. 30.. Sensors and Actuators 1997. T. Lee.. Tachikawa. 2006. Lee. J. Kim. T.... 3801. W.. Kwon. Lee. Hasan. Lee. D. 2002. Soc. Am. 19.-M. R.. R. 16. Soc. J.. Tanaka. Soh. Beckman. Yoo. Lee. Chem. 14. A.. Ahn.. M. Yoon.. B... 124. Roy. Yoon. D. 2008. 13. Bowen. Res.-M.. V.. D. Okada. R. Rev. 18. Habets. H. 11.-J... Soc... 179. Song. Chem. 565. R. McGraw-Hill.. S. 3887. 20. . R. 2005. N. M.. H. Derby. Whitfield. R. Suh. Anal. 47... Am. E. 5010. 23. 26.. 13. Y. Eo. Yoon. Y. 130.. Lee. 2009... Hibra... P. Chem. J. Kim.1756 Bull.. K. Burns. Chem. S. Anne. K.. A 2000. 4117. 3674. Peng. M. M. E. 27. Am. C. Lagally. Kurz. Y. Convective Heat and Mass Transfer. H. Acc.. 16. 1. Nam. Kim. A. N.-H. D. P. Kim. H. J. Kim. Lee. K. Gaitan.. 25.-W. 872. A.. Angew. Sasaki. Ed. Korean Chem. 29. Kou. 1993. Kays.. Adv. 894. Adv. 31.... J. Chem.-S. 78. D. Anal. S. 20. Cristini. Kim. 31. M. Slyadnev. Charych. R. 15. D. 6 Notes 21. Chromatogr. 396. Sci. Macromolecules 1980. K. 2010. W. Rimai. 2006. Int. 4432. Kim. S. Mater. 2001.. K. J. J. S. S. S. A. B. S.. J. J. van Noort. 1690. 17. 2008. Swamy. 12. Yang. 2001. 17580. 2. 127. Mater. C. Park. H. D. A. H. 2008.-C. Electronic Thesis and Dissertation Library.. Inc: New York. J. E. B. A. S.. R.. J. Kim. S. Spevak. Manz. H. Ross. Sens. 45. 2947. Anal. W. Chem.-M. A.. H. 22. 350. Lee... J.. H. J. Yang. Park. 131.. Soc. Y. M. M. I. Ryu. Song. 2009. Bluhm. Jun. S. 114. Tan. Chance. P.. 73. 1993. Dittrich. Y.
This action might not be possible to undo. Are you sure you want to continue?
We've moved you to where you read on your other device.
Get the full title to continue reading from where you left off, or restart the preview.