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Volumn 79, Issue 21, 2007, Pages 8222-8231

Fourier analysis to measure diffusion coefficients and resolve mixtures on a continuous electrophoresis chip

Author keywords

[No Author keywords available]

Indexed keywords

DIFFUSION IN SOLIDS; ELECTRIC FIELD EFFECTS; ELECTROPHORESIS; FOURIER TRANSFORMS; MOLECULAR MASS; TWO DIMENSIONAL;

EID: 35848961243     PISSN: 00032700     EISSN: None     Source Type: Journal    
DOI: 10.1021/ac070532z     Document Type: Article
Times cited : (19)

References (60)
  • 8
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    • Stilbs, P. Anal. Chem. 1981, 53, 2135-2137.
    • (1981) Anal. Chem , vol.53 , pp. 2135-2137
    • Stilbs, P.1
  • 24
    • 35848965533 scopus 로고    scopus 로고
    • The velocity field of the species F can be essentially considered as constant along 2 in the whole device (vide infra). As the F concentration at the injection point is also independent on z, the problem is rigorously bidimensional.
    • The velocity field of the species F can be essentially considered as constant along 2 in the whole device (vide infra). As the F concentration at the injection point is also independent on z, the problem is rigorously bidimensional.
  • 25
    • 35848964429 scopus 로고    scopus 로고
    • 2t).
    • 2t).
  • 31
    • 0036111913 scopus 로고    scopus 로고
    • The front position was calculated by correlating each intensity profile with its symetric. See, for example
    • The front position was calculated by correlating each intensity profile with its symetric. See, for example: Gosse, C.; Croquette, V. Biophys. J. 2002, 82, 3314-3329.
    • (2002) Biophys. J , vol.82 , pp. 3314-3329
    • Gosse, C.1    Croquette, V.2
  • 32
    • 35848957521 scopus 로고    scopus 로고
    • j,n extraction.
    • j,n extraction.
  • 33
    • 35848936990 scopus 로고    scopus 로고
    • The whole pool of normalized Fourier modes was appropriate for mixture analysis. All the normalized Fourier modes are fitted in parallel with a monoexponential and a biexponential function. All the modes giving satisfactory residuals with the simpler fit were discarded, the parameters extracted from their biexponential analysis being considered unreliable (Figure S-9).
    • The whole pool of normalized Fourier modes was appropriate for mixture analysis. All the normalized Fourier modes are fitted in parallel with a monoexponential and a biexponential function. All the modes giving satisfactory residuals with the simpler fit were discarded, the parameters extracted from their biexponential analysis being considered unreliable (Figure S-9).
  • 34
    • 35848961953 scopus 로고    scopus 로고
    • The Gaussian shape reflects the channel one broadened by molecular diffusion and migration due to out-of-axis electric fields between the injection nozzle and the zone of homogeneous velocity see Supporting Information
    • The Gaussian shape reflects the channel one broadened by molecular diffusion and migration due to out-of-axis electric fields between the injection nozzle and the zone of homogeneous velocity (see Supporting Information).
  • 39
    • 35848943943 scopus 로고    scopus 로고
    • The bowed channels located on the injection side of the device were shortened to compensate for width reduction, thus keeping their overall resistance constant
    • The bowed channels located on the injection side of the device were shortened to compensate for width reduction, thus keeping their overall resistance constant.
  • 40
    • 35848931938 scopus 로고    scopus 로고
    • Electric potential profiles were calculated by finite element method simulations and found in good agreement with this estimate. The electric field is constant and directed along the x-axis everywhere beyond a l0, 40 μm limit inside the chamber boundaries Figure S-7, We checked on chip these predictions by recording the migration of long and thin bands of YOYO-1-stained 1257-bp dsDNA When prepared along y and eluted in the x direction, a stripe of this weakly diffusing fluorophore moves straight and stays normal to u→x, thus confirming the field homogeneity and direction
    • x, thus confirming the field homogeneity and direction.
  • 41
    • 35848933301 scopus 로고    scopus 로고
    • The pillars that sustain the PDMS chamber ceiling also induce a perturbation of the electric potential. However, it is of the order of their diameter (i.e, 30 μm) and exerts no significant influence on the analyte migration
    • The pillars that sustain the PDMS chamber ceiling also induce a perturbation of the electric potential. However, it is of the order of their diameter (i.e., 30 μm) and exerts no significant influence on the analyte migration.
  • 47
    • 1242328691 scopus 로고    scopus 로고
    • By comparing the fluorescein electrophoretic velocity in the two media, the remaining electroosmotic mobility μEO in 0.1, PDMA was evaluated to be less than 10% of the apparent electrophoretic mobility for all the considered analytes; see ref 43 and: Zhang, P, Ren, J. Anal Chim. Acta 2004, 507, 179-184
    • EO in 0.1 % PDMA was evaluated to be less than 10% of the apparent electrophoretic mobility for all the considered analytes; see ref 43 and: Zhang, P.; Ren, J. Anal Chim. Acta 2004, 507, 179-184.
  • 48
    • 35848953250 scopus 로고    scopus 로고
    • To quantify the electroosmotic dispersive contribution that could superimpose to Brownian diffusion, we designed a series of control time-based experiments where the apparent diffusion coefficients are extracted from the time evolution along the y-axis of an x-invariant concentration profile. Measurements were performed either in the absence or in the presence of a transverse alternative electric field Ey (see Supporting Information).7,45 For the two filling media, the good agreement between the apparent diffusion coefficients extracted from time-based as well as continuous experiments strongly supports the absence of any significant electric field-induced dispersion in the present systems
    • 7,45 For the two filling media, the good agreement between the apparent diffusion coefficients extracted from time-based as well as continuous experiments strongly supports the absence of any significant electric field-induced dispersion in the present systems.
  • 49
    • 35848932138 scopus 로고    scopus 로고
    • As evaluated from Mark-Houwink parameters (Heller, C. Electrophoresis 1999, 20, 1962-1977, 0.1, w/w) PDMA approximately corresponds to the entanglement threshold for the 3-MDa polymer. Thus, slight viscosity or steric effects might be present
    • As evaluated from Mark-Houwink parameters (Heller, C. Electrophoresis 1999, 20, 1962-1977), 0.1 % (w/w) PDMA approximately corresponds to the entanglement threshold for the 3-MDa polymer. Thus, slight viscosity or steric effects might be present.
  • 57
    • 0034671973 scopus 로고    scopus 로고
    • In the present approach, the differentiation between two species Fj relies on their respective Dj/ν xj ratio. Using the Einstein equation Dj, kT/ξj, the expressions of the electrophoretic mobility μj, zj/ξj and of the velocity ν→j, νxju→ x, μj, μEO Exu→x, this discriminating factor develops as Dj/νxj, kT/[(zj, μEO ξj)Ex, where ξj and zj are the respective Fj solute molecular friction coefficient and charge. In principle, it should consequently always be possible to discriminate the two components in a binary mixture. Indeed, even when
    • j.
  • 58
    • 35848949136 scopus 로고    scopus 로고
    • A sum of two Gaussian functions failed to fit the stationary migration, diffusion pattern in the direct space, thus emphasizing the strength of Fourier data analysis
    • A sum of two Gaussian functions failed to fit the stationary migration - diffusion pattern in the direct space, thus emphasizing the strength of Fourier data analysis.
  • 59
    • 35848931283 scopus 로고    scopus 로고
    • From independent bulk measurements, we estimated the chemical relaxation time for all the injected duplexes to be at least 1 order of magnitude longer than the analysis duration. Consequently, the present technique provides information on the composition of the reactive mixture, which can be considered as frozen at equilibrium.
    • From independent bulk measurements, we estimated the chemical relaxation time for all the injected duplexes to be at least 1 order of magnitude longer than the analysis duration. Consequently, the present technique provides information on the composition of the reactive mixture, which can be considered as frozen at equilibrium.


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