Analytical Chemistry Chemical Cytometry Quantitates Superoxide

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Figure 4. Resolution of commercially available mixtures of (Pi)n. Samples consisting of commercially available mixtures of polyphosphate glass (20 mM in total phosphate, Na + salt) and CH3SO3 - (2 mM) were analyzed by CGE. After electrokinetic injection (4.0 s at 10 kV), (Pi)n were separated by electrophoresis at 14.6 kV in coated capillaries (57 cm in length, 50 cm between inlet and detector) filled with solutions of 9.1% PDMA (w/v) and running buffer (24.0 mM tris, 3.0 mM TP 2- ,pH) 8.4). Peaks in trace C, for n ∼ 10-40, appear less sharp than the peaks in other runs. The reason for this difference is unclear; one possibility is that the peaks are affected by irregularities in pH within capillaries during separation, caused by a small mismatch in pH between samples (∼8) and the running buffer (pH ) 8.4). 72 in phosphate residues; n¯ ∼ 17) and added P3, P4, P6, P8, orP10 (2.0 mM). The x-axis of traces in Figure 3 are in units of mobility relative to CH3SO3 - µp,rel (eq 1). The traces show the alignment of peaks from run to run and allowed us to assign peaks with increased area to specific (Pi)n (dotted lines in Figure 3). The dotted line for n ) 20 in Figure 3B is based on the reasonable assumption that the peaks continue in order of n. 71 Mixtures of (Pi)n with n up to ∼70. The CGE data in Figure 4 characterizes commercially available mixtures of (Pi)n with different distributions in chain length. Samples analyzed in traces A-D are in order of increasing average chain length. The results show that peaks with n up to ∼70 can be resolved in a single run; longer (Pi)n may potentially be resolved using lower concentrations of PDMA. Shapes of Peaks. The asymmetric peaks observed in both CZE and CGE experiments are typical for electropherograms collected by indirect UV absorbance. (Pi)n with mobility greater than that of TP 2- shows up as peaks broadened to the left, while (Pi)n with mobility less than that of TP 2- show up as peaks broadened to the right. These shapes are the results of dispersion by electromigration, originating from (i) differences in mobility between analytes and TP 2- and (ii) nonuniform electric fields inside sample zones. Discussion of the origin of the shapes of peaks is available in the Supporting Information, as well as in ref 59. Quantitative Analysis of (Pi)n: Areas of Peaks. Three contributions determine the area of a peak: (i) the response of [TP 2- ]to(Pi)n; (ii) the amount of (Pi)n transferred from the sample to the capillary by electrokinetic injection; (iii) residence time of the analyte passing the detector. Analysis of the areas of peaks for (Pi)n and CH3SO3 - enables the quantification of resolved (Pi)n. To account for the effect of (iii), areas of peaks are adjusted by the factor (1/ti), where t is the retention time of analyte i. 73 In eq 2, the ratio of adjusted areas for analyte i and CH3SO3 - (Ai and ACH3SO3 -) is related to the concentrations [i]S and [CH3SO3 - ] of the sample: zi and zCH3SO3 - are the electrostatic charge of i and CH3SO3 - ; µCH3SO3 - and µi are the mobilities of i and CH3SO3 - ; µC + is the mobility of the cation in the sample zone (bis-tris-H + or tris-H + ). A i A CH3 SO 3 - [i] S ) [CH3SO3 - ] · [ z i z CH3 SO 3 -] · µ + µ C+ i [ µ + µ C+ CH3SO -] 3 (2) The Supporting Information contains our derivation of eq 2 and a discussion of the quantitative aspects of electrokinetic injection and indirect UV absorbance. Equation 2 reveals the advantage of analyzing electropherograms by comparing peaks for (Pi)n and CH3SO3 - . The ratio (Ai/ ACH3SO3 -) depends on the ratio ([i]S/[CH3SO3 - ]) but does not depend on the concentration of other ions in the sample or the voltage and duration of electrokinetic injection. Calibration of Peak Areas to Concentrations of P1, P2, P3, and cyclo-P3. Analysis of samples of containing P1, P2, P3, or cyclo-P3 and added CH3SO3 - by CZE demonstrated the relationship between peak areas and concentrations. Figure 5 shows values of (Acyclo-P3 /ACH3SO3 -) determined from the analysis of samples containing cyclo-P3 and CH3SO3 - . Samples had ratios (71) The alignment is not perfect; small differences from run to run are possibly due to dispersion in electromigration, caused by differences between samples in pH or ionic strength. (72) Another possibility is that electrokinetic injections may result in concentrations of (Pi)n at the inlet that can lead to precipitation. (73) Hilser, V. J.; Freire, E. Anal. Biochem. 1995, 224, 465–485. 6844 Analytical Chemistry, Vol. 82, No. 16, August 15, 2010
Figure 5. Quantitative calibration of cyclo-P3. The plot shows values for Acyclo-P3 /ACH3SO3 - determined in the analysis of cyclo-P3 and CH3SO3 - by CZE, using coated capillaries (57 cm in length, 50 cm between inlet and detector) filled with running buffer (18.0 mM bis-tris, 3.0 mM TP2- ,pH) 6.9). Points for ([cyclo-P3]/[CH3SO3 - ]) ) 0.1, 1.0, or 10.0 are the average taken from eight experiments. Standard deviations for (Acyclo-P3 /ACH3SO3 -) are 40 and distinguished the composition of mixtures generated at 125 and 140 °C. Cyclo-P3 is the most abundant species in mixtures prepared at 140 °C. In contrast, the mixture prepared at 125 °C does not contain cyclo-P3, despite containing linear (Pi)n with n > 40. The reason for the Analytical Chemistry, Vol. 82, No. 16, August 15, 2010 6845
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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
Page 49 and 50: Table 1. Extraction Yields, Liquid
Page 51 and 52: scanning of AMPP amides of the anal
Page 53 and 54: Anal. Chem. 2010, 82, 6797-6806 δ
Page 55 and 56: Figure 1. Schematic view of the pre
Page 57 and 58: from the specimen and enclosed in a
Page 59 and 60: Figure 4. (A) IRMS mass-44 chromato
Page 61 and 62: Table 3. Ambient Measurement Result
Page 63 and 64: Anal. Chem. 2010, 82, 6807-6813 Dir
Page 65 and 66: Polymerase (1 U per sample). Reacti
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Page 75 and 76: Table 2. Concentrations and Ratios
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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
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Page 97 and 98: constant medium for separation; we
Page 99: Figure 2. Standards of (Pi)n, n ) 1
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
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Page 123 and 124: Table 1. Absolute Quantification Re
Page 125 and 126: ment. Therefore, the long-time drea
Page 127 and 128: Figure 1. Chemically actuated micro
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
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Anal. Chem. 2010, 82, 6895-6903 Ele
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Table 1. Chemical Structure, pKa Va
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pH with a tilted baseline (Figure 1
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Table 2. Linearity and Detection Li
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ascorbic acid (AA), uric acid (UA),
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the multielement capabilities, the
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RESULTS AND DISCUSSION Sulfur Detec
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Table 2. Molecular Properties and C
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Anal. Chem. 2010, 82, 6911-6918 Dir
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dilution and hybridization buffer.
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solution under appropriate incubati
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Figure 4. Standardization curve for
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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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Analytical Chemistry Chemical Cytometry Quantitates Superoxide

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