Analytical Chemistry Chemical Cytometry Quantitates Superoxide

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Anal. Chem. 2010, 82, 6870–6876 Autonomous Microfluidic Control by Chemically Actuated Micropumps and Its Application to Chemical Analyses Atsushi Takashima, Kenichi Kojima, and Hiroaki Suzuki* Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan Autonomous control of microfluidic transport was realized through the use of chemically actuated diaphragm micropumps connected to a network of controlling flow channels. A hydrogen peroxide (H 2O2) solution was transported in the controlling flow channel by capillary action. Upon the solution’s arrival at the lower compartment of a micropump filled with manganese dioxide (MnO 2) powder, a volume change that accompanied the production of oxygen caused by the catalytic decomposition of H 2O2 induced inflation of the diaphragm. This in turn caused the movement of a solution in another network of flow channels formed in the upper layer. Micropumps that only exert pressure were also fabricated. By positioning the micropumps at appropriate locations in conjunction with additional flow-delaying components, the ejection of solutions from the reservoir of each micropump could be initiated at coordinated times. Furthermore, the solutions could be transported by the application of pressure from other micropumps. In other words, the information for switching from one micropump to another could be described on the chip in the form of a network of flow channels. This autonomous processing of solutions was demonstrated for enzymatic analyses of H 2O2, glucose, and lactate. With the progress now being made in microfluidic technologies, innovative devices that make possible the complicated manipulation of solutions have been proposed for various applications. 1-5 However, as far as microfluidic transport is concerned, many of these previous devices have relied on external instruments such as microsyringe pumps or power sources to produce pressure-driven flows or to generate electroosmotic flows. Such bulky instruments, however, are obstacles to the increased integration of components and miniaturization of the entire system. * To whom correspondence should be addressed. Phone: +81-29-853-5598. Fax: +81-29-853-4490. E-mail: hsuzuki@ims.tsukuba.ac.jp. (1) Thorsen, T.; Maerkl, S. J.; Quake, S. R. Science 2002, 298, 580–584. (2) Balagaddé, F. K.; You, L.; Hansen, C. L.; Arnold, F. H.; Quake, S. R. Science 2005, 309, 137–140. (3) Shiu, J.-Y.; Chen, P. Adv. Mater. 2005, 17, 1866–1869. (4) Wang, C.-H.; Lee, G.-B. Biosens. Bioelectron. 2005, 21, 419–425. (5) Satoh, W.; Hosono, H.; Yokomaku, H.; Morimoto, K.; Upadhyay, S.; Suzuki, H. Sensors 2008, 8, 1111–1127. 6870 Analytical Chemistry, Vol. 82, No. 16, August 15, 2010 To address this problem, trials have been performed to integrate active microfluidic components on a single chip. 6-10 The long history of the development of micropumps and microvalves has produced a variety of devices that are based on various principles. 11-13 In the reported devices, actuation of the components has usually been based on switching by electrical signals that are programmed in a number of ways. In this approach, however, specially designed electronic circuits and software are needed to realize cooperative operation of the components. In addition, for disposable devices, it would be preferable for the microfluidic system to function autonomously. To resolve this problem, chemical actuators that are based upon the spontaneous volume change of a hydrogel have been reported. 14-16 Capillary action has also been used to realize a variety of devices for the autonomous transport of solutions and various other applications. 17-23 These previous approaches, particularly the latter one, suggest a direction for the realization of more sophisticated devices in the next generation. The manipulation of solutions in devices has been based on programmed instructions described on the chip as a structural (6) Choi, J.-W.; Oh, K. W.; Han, A.; Okulan, N.; Wijayawardhana, C. A.; Lannes, C.; Bhansali, S.; Schlueter, K. T.; Heineman, W. R.; Halsall, H. B.; Nevin, J. H.; Helmicki, A. J.; Henderson, H. T.; Ahn, C. H. Biomed. Microdevices 2001, 3, 191–200. (7) Srinivasan, V.; Pamula, V. K.; Fair, R. B. Lab Chip 2004, 4, 310–315. (8) Satoh, W.; Hosono, H.; Suzuki, H. Anal. Chem. 2005, 77, 6857–6863. (9) Nashida, N.; Satoh, W.; Fukuda, J.; Suzuki, H. Biosens. Bioelectron. 2007, 22, 3167–3173. (10) Abdelgawad, M.; Wheeler, A. Adv. Mater. 2009, 21, 920–925. (11) Gravesen, P.; Branebjerg, J.; Jensen, O. S. J. Micromech. Microeng. 1993, 3, 168–182. (12) Shoji, S.; Esashi, M. J. Micromech. Microeng. 1994, 4, 157–171. (13) Laser, D. J.; Santiago, J. G. J. Micromech. Microeng. 2004, 14, R35–R64. (14) Beebe, D. J.; Moore, J. S.; Yu, Q.; Liu, R. H.; Kraft, M. L.; Jo, B.-H.; Devadoss, C. Proc. Natl. Acad. Sci. U.S.A. 2000, 97, 13488–13493. (15) Suzuki, H.; Kumagai, A.; Ogawa, K.; Kokufuta, E. Biomacromolecules 2004, 5, 486–491. (16) Suzuki, H.; Tokuda, T.; Kobayashi, K. Sens. Actuators, B 2002, 83, 53–59. (17) Zhao, B.; Moore, J. S.; Beebe, D. J. Science 2001, 291, 1023–1026. (18) Ahn, C. H.; Choi, J.-W.; Beaucage, G.; Nevin, J. H.; Lee, J.-B.; Puntambekar, A.; Lee, J. Y. Proc. IEEE 2004, 92, 154–173. (19) Bouaidat, S.; Hansen, O.; Bruus, H.; Berendsen, C.; Bau-Madsen, N. K.; Thomsen, P.; Wolff, A.; Jonsmann, J. Lab Chip 2005, 5, 827–836. (20) Delamarche, E.; Juncker, D.; Schmid, H. Adv. Mater. 2005, 17, 2911– 2933. (21) Chung, K. H.; Hong, J. W.; Lee, D.-S.; Yoon, H. C. Anal. Chim. Acta 2007, 585, 1–10. (22) Zimmermann, M.; Hunziker, P.; Delamarche, E. Microfluid. Nanofluid. 2008, 5, 395–402. (23) Swickrath, M. J.; Burns, S. D.; Wnek, G. E. Sens. Actuators, B 2009, 140, 656–662. 10.1021/ac1009657 © 2010 American Chemical Society Published on Web 07/29/2010
Figure 1. Chemically actuated micropumps with flow channels. (A) Exploded view of the micropumps and the flow channels. (B) Operation of the micropump. Cross-sections are shown that include the flow channel for transport, the diaphragm, and the lower compartment for the H2O2 solution. First, the reservoir of the micropump is filled with a solution to be transported (top). When a H2O2 solution is transported in the controlling flow channel and reaches the lower compartment of the micropump, bubbles are produced, the diaphragm inflates, and the solution in the upper reservoir is injected into the upper flow channel (bottom). arrangement of components, including the flow channel network. 18 Although there have been limitations in manipulation that is performed only through capillary action, even the complicated manipulation of solutions may be realized by coupling a programmed microfluidic network with chemically actuated microfluidic components. In a number of previous studies, gas bubbles produced by the electrolysis of water were used to produce a volume change that would mobilize a solution in a microflow channel. 24-29 This principle of operation is attractive for the realization of a chemically actuated micropump, because gas production is accompanied by many chemical reactions. In creating our device, we used the volume change of oxygen bubbles produced by the catalytic decomposition of H2O2. 26 To trigger the pumping action, a H2O2 solution was transported and supplied to the micropumps by capillary action in a controlling flow channel. A network of controlling flow channels described on a chip could be used as a program to operate many micropumps cooperatively. In other words, the timing of the switching among pumps could be adjusted by changing the relative positions of the micropumps and the length or other dimensional parameters of the flow channels. In this paper we present the basic concept for a chemically actuated micropump and its programming and characterize the performance of the device. (24) Böhm, S.; Timmer, B.; Olthuis, W.; Bergveld, P. J. Micromech. Microeng. 2000, 10, 498–504. (25) Suzuki, H.; Yoneyama, R. Sens. Actuators, B 2003, 96, 38–45. (26) Choi, Y. H.; Son, S. U.; Lee, S. S. Sens. Actuators, A 2004, 111, 8–13. (27) Satoh, W.; Shimizu, Y.; Kaneto, T.; Suzuki, H. Sens. Actuators, B 2007, 123, 1153–1160. (28) Shimizu, Y.; Takashima, A.; Satoh, W.; Sassa, F.; Fukuda, J.; Suzuki, H. Sens. Actuators, B 2009, 140, 649–655. (29) Blanco-Gomez, G.; Glidle, A.; Flendrig, L. M.; Cooper, J. M. Anal. Chem. 2009, 81, 1365–1370. EXPERIMENTAL SECTION Materials and Reagents. A thick-film photoresist (SU-8) was purchased from MicroChem, Newton, MA. A precursor solution of poly(dimethylsiloxane) (PDMS) (KE-1300T) was purchased from Shin-Etsu Chemical, Tokyo, Japan. A precursor solution of PVA-SbQ, SPP-H-13, was purchased from Toyo Gosei Kogyo, Chiba, Japan. H2O2, manganese dioxide, and poly(oxyethylene) sorbitan monolaurate (Tween 20) were purchased from Wako Pure Chemical Industries, Osaka, Japan. The enzymes and related reagents were obtained from the following commercial sources: horseradish peroxidase (HRP; 100 U/mg), lactate oxidase (LOD; 38 U/mg), and bovine serum albumin (BSA) from Wako Pure Chemical Industries, Osaka, Japan; glucose oxidase (GOD; 151 U/mg) and 25% glutaraldehyde (GA) solution from Sigma-Aldrich, St. Louis, MO; N-acetyl-3,7dihydroxyphenoxazine (Amplex Red) from AnaSpec, San Jose, CA. Basic Structure and Fabrication of the Microfluidic Devices. The devices were constructed by stacking two PDMS substrates on a glass substrate (Figure 1). Flow channels were formed with PDMS using a template formed with a thick-film photoresist (SU-8). The compartments for the pumps and solutions to be transported were formed in the lower and upper PDMS layers by punching. A critical part of each micropump was a circular compartment (diameter 2.5 mm) with a diaphragm. The diaphragm was formed by intercalating a 50 µm thick PDMS sheet between the two PDMS substrates. The lower part of the compartment was connected to a controlling flow channel for the transport of a H2O2 solution. To form a MnO2 layer in the vicinity of the diaphragm, a droplet of water containing a suspension of MnO2 powder was put into the compartment that was then placed upside Analytical Chemistry, Vol. 82, No. 16, August 15, 2010 6871
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Anal. Chem. 2010, 82, 6745-6750 Let
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purchased from Invitrogen-Molecular
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Figure 3. Electropherograms of TPP-
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Anal. Chem. 2010, 82, 6751-6755 Res
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(pH 8.0) with cysteine and cystamin
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Figure 4. Ion mobility mass spectra
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GOx glucose + O298 gluconic acid +
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coater at 2000 rpm for 20 s, and th
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Figure 5. Comparison of cyclic volt
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in channels with either no grooves
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indicators of atmospheric processin
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Figure 1. GC/MS total ion chromatog
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Table 2. Concentrations and Stable
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on a substrate are preferred. 20-24
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Figure 4. SERS analysis of NAADP co
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Anal. Chem. 2010, 82, 6775-6781 Hig
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tion, 2 µL of proprionaldehyde wer
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Figure 4. Analysis of 2a by HPLC-MS
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eaction of 1a with PBH can be condu
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Numerous references had demonstrate
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Figure 1. TEM images of the prepare
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Figure 4. Schematic representation
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esult in a big SPR signal change wi
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also reduces chemical noise, which
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Table 1. Extraction Yields, Liquid
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scanning of AMPP amides of the anal
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Anal. Chem. 2010, 82, 6797-6806 δ
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Figure 1. Schematic view of the pre
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from the specimen and enclosed in a
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Figure 4. (A) IRMS mass-44 chromato
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Table 3. Ambient Measurement Result
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Anal. Chem. 2010, 82, 6807-6813 Dir
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Polymerase (1 U per sample). Reacti
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of which was constant for all ampli
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analytically useful signals at less
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carbon black and RP-C18 for the ext
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solution in an equal volume, and 1
Page 75 and 76: Table 2. Concentrations and Ratios
Page 77 and 78: Anal. Chem. 2010, 82, 6821-6829 Mac
Page 79 and 80: mg/mL protein, followed by separati
Page 81 and 82: Figure 2. Productivity of SEQUST an
Page 83 and 84: Figure 4. High-resolution MS/MS spe
Page 85 and 86: Figure 6. Characterization of PSMs
Page 87 and 88: containing T-T mismatches. 23 Based
Page 89 and 90: Figure 1. Extinction spectra of sol
Page 91 and 92: Figure 3. (A) The value of Ex650 nm
Page 93 and 94: Figure 5. Extinction spectra and co
Page 95 and 96: wished to explore the dehydration o
Page 97 and 98: constant medium for separation; we
Page 99 and 100: Figure 2. Standards of (Pi)n, n ) 1
Page 101 and 102: Figure 5. Quantitative calibration
Page 103 and 104: Anal. Chem. 2010, 82, 6847-6853 Met
Page 105 and 106: Figure 1. 226 Ra spectrum by liquid
Page 107 and 108: Table 1. Counting Properties and De
Page 109 and 110: Table 3. Analysis of 226 Ra in Sedi
Page 111 and 112: mercial microarray scanner and fabr
Page 113 and 114: Figure 2. Optical transmission meas
Page 115 and 116: Figure 5. Volcano plots detailing t
Page 117 and 118: data as well. The 41 genes in Table
Page 119 and 120: corresponding compound if its chemi
Page 121 and 122: Figure 1. Schematic illustration of
Page 123 and 124: Table 1. Absolute Quantification Re
Page 125: ment. Therefore, the long-time drea
Page 129 and 130: Figure 2. Influence of a surfactant
Page 131 and 132: Figure 5. Device to eject and mix s
Page 133 and 134: Anal. Chem. 2010, 82, 6877-6886 Imm
Page 135 and 136: NaCl, phosphate buffer saline (PBS)
Page 137 and 138: Figure 2. Product ion mass spectra
Page 139 and 140: -70 °C resolved the problem, givin
Page 141 and 142: Table 1. Intraday Precision and Acc
Page 143 and 144: Anal. Chem. 2010, 82, 6887-6894 Fer
Page 145 and 146: Figure 1. Infrared spectra of (A) u
Page 147 and 148: Figure 3. Cyclic voltammograms obta
Page 149 and 150: Figure 6. Calculated charge from ch
Page 151 and 152: Anal. Chem. 2010, 82, 6895-6903 Ele
Page 153 and 154: Table 1. Chemical Structure, pKa Va
Page 155 and 156: pH with a tilted baseline (Figure 1
Page 157 and 158: Table 2. Linearity and Detection Li
Page 159 and 160: ascorbic acid (AA), uric acid (UA),
Page 161 and 162: the multielement capabilities, the
Page 163 and 164: RESULTS AND DISCUSSION Sulfur Detec
Page 165 and 166: Table 2. Molecular Properties and C
Page 167 and 168: Anal. Chem. 2010, 82, 6911-6918 Dir
Page 169 and 170: dilution and hybridization buffer.
Page 171 and 172: solution under appropriate incubati
Page 173 and 174: Figure 4. Standardization curve for
Page 175 and 176: Anal. Chem. 2010, 82, 6919-6925 Ele
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the ×10 objective, to have a large
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Figure 2. With a suitable removal o
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the NB signal in a much better foot
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Scheme 1. Reactions of Selenium Rea
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Figure 2. (a) ESI-MS spectrum showi
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Figure 4. (a) ESI-MS spectrum showi
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Anal. Chem. 2010, 82, 6933-6939 Dif
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trode 28 by a finite element using
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Figure 4. Comparison between simula
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Figure 6. Comparison between simula
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educed in the vicinity of double bo
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Figure 2. Normalized product ion ab
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Figure 4. EID (a) and IRMPD (b) of
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Anal. Chem. 2010, 82, 6947-6957 Ide
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Figure 1. Schematic flowchart showi
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difference, ppm compound Table 1. I
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isoforms, its successful use, in th
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Figure 5. Extracted ion current ESI
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m/z 1172.935 was observed for Ser14
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linked products via affinity tags.
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Scheme 2. Fragmentation Mechanism o
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Figure 1. (A) ESI-LTQ-CID-MS 2 prod
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Figure 3. (A) ESI-LTQ-CID-MS 2 prod
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Figure 5. (A) MALDI-TOF/TOF product
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Anal. Chem. 2010, 82, 6969-6975 Ana
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Figure 3. Equilibrium response as a
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Figure 6. The average measured resp
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for the fill time, and we find that
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nucleotide tails. 3-5 Thus, the amo
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allow the use of higher aptamer con
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quent ligation of the aptamers afte
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Anal. Chem. 2010, 82, 6983-6990 Imp
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Figure 2. Configuration editor wind
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Figure 4. Dependencies between volu
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Since the time for liquid expulsion
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Anal. Chem. 2010, 82, 6991-6999 Int
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Figure 1. Representation of the Car
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Table 2. Capillary Electrophoresis
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Figure 4. (A) Typical raw electroph
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field. DNA profiles were delivered
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Another approach to handle this lim
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(principal components, PCs) in whic
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Figure 5. Relevant score plots and
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CONCLUSIONS In this paper we have i
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electroactive-species loaded liposo
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Figure 2. Qdot-based FLFTS response
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Figure 6. Fluorescence imaging of Q
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Anal. Chem. 2010, 82, 7015-7020 Sel
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Table 1. Effect of 1 D-LC Condition
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Figure 3. Peak-production rate vers
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Anal. Chem. 2010, 82, 7021-7026 Cel
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luciferase (T7 control vector) was
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Figure 3. Inhibitory effects of luc
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Anal. Chem. 2010, 82, 7027-7034 Pat
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Electrochemistry. Electrochemical m
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Figure 2. SEM images of Au substrat
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Table 3. Film Thickness Measurement
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Anal. Chem. 2010, 82, 7035-7043 Qua
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Figure 1. (A) FL spectra of BSPOTPE
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Figure 4. (A) Variation in the FL i
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Figure 6. (A) FL spectra of BSPOTPE
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Scheme 1. Proposed Mechanism for Fl
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one or more drawbacks including poo
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Figure 2. Free fluorophores do not
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Anal. Chem. 2010, 82, 7049-7052 Dev
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Figure 2. Comparative analysis of d
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