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Integrated Microfluidics <download slide pdf>
One important goal of our program
is to establish intelligent control of molecular transport in space and time at
small length scales.Intelligent control
implies materials and structures that can sense molecular characteristics,
e.g. size, charge, molecular shape, etc., and then generate control signals
that control transport based on those molecular characteristics. Specifically we seek to manipulate,
(separate, isolate, react, detect) low-mass samples with the same precision and
level of control currently possible with bench-scale samples by combining
microfluidic and nanofluidic structures to achieve integrated microfluidics capable of addressing the challenging
problems posed by multi-dimensional
separations and analysis with low mass samples.
Molecular transport in structures
of nanometer (1 nm <d < 100
nm) characteristic dimensions is a critical component of a large number of
separation technologies and sensor paradigms. Independent of the type of force
field used to drive transport, the unique characteristics of nanoscale
structures ensure that transport is fundamentally different than in larger mm and mm-scale structures. The
similarity of the Debye length, and the channel diameter, accesses a new electrokinetic flow
regime ka ~ 1), that is not available at longer lengthscales, even in mm-scale capillaries. By changing
k-1 it is possible to move from a regime, ka >> 1, where flow is dominated by
electrophoresis to a regime, ka ~ 1, where electroosmotic flow is the
dominant transport mechanism. This is possible, because in the nanochannels
there is a preponderance of counterions over co-ions; in fact it is easy to
achieve conditions where every mobile counterion in the pore is of one polarity, i.e. there are no co-ions.
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Multidimensional Chemical Analysis of Mass Limited Samples <download slide pdf>
Two sample types naturally demand
that samples be handled in low masses: (a) availability-limited samples – where
the mass is limited by the inherent amount of sample available for
characterization, and (b) attribute-limited samples - where the mass is limited
by some characteristic, e.g. toxicity
or cost, of the analyte. Key to the concept of manipulating small-mass analyte
“packets” for multidimensional analysis is the ability to move exceptionally
small fluidic volume elements (voxels) to desired physical locations at desired
times with high precision and with flexible control elements.Skoog et
al. define the unit operations of chemical analysis at the bench scale
(weighing, volume measurement, filtration, etc. and an analogous set of operations could be defined
for low-mass analyses including, for example: (a) separation, (b) isolation,
(c) reaction, and (d) detection.
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Nanofluidics <download slide pdf>
The vast preponderance of studies
of fluid transport in nanocapillary array membranes (NCAMs) rely on composite
measurements over an ensemble of pores. We take up the quantitative characterization of nanopore flow using
single nanopores as a uniquely powerful experimental model system. NCAMs,
containing 10 8-10 9 pores cm -2, are naturally
characterized by dispersion in the pore characteristics, e.g. different pores have slightly different angles relative to the
surface plane, and therefore slightly different lengths; the pores do not have
uniform diameters along their length, i.e. they are not strictly cylindrical; and over sufficiently large areas, defects,
such as branched pores, always exist. To circumvent these difficulties we have
developed a 4 p microscope capable of
individually detecting single molecules at the entrance and the exit of a membrane containing a single cylindrical nanopore. The dual confocal single-molecule-counting 4 p microscope is comprised of two identical, axially opposed single-molecule
sensitivity laser-induced fluorescence microscopes. This arrangement allows photon bursts from
the entrance and exit channels to be cross-correlated in time to tease out
velocities of individual probe molecules.
For more information about these
efforts, please see the graphics gallery that follows and these original
papers:
Kemery, P.J.; Steehler, J.K.;
Bohn, P.W. “Electric Field Mediated Transport in Nanometer Diameter Channels,” Langmuir 1998, 14, 2884-2889.
Kuo, T.C.; Sloan, L.A.;
Sweedler, J.V.; Bohn, P.W. “Manipulating Molecular Transport Through Nanoporous
Membranes by Control of Electrokinetic Flow: Effect of Surface Charge Density and Debye Length,” Langmuir, 2001, 17,
6298-6303.
Kuo,
T.C.; Cannon, D.M. Jr.; Feng, W.; Shannon, M.A.; Sweedler, J.V; Bohn, P.W.
“Gateable Nanofluidic Interconnects in Multilevel Microanalytical Systems,” Analyt. Chem. 2003, 75, 1861-1867.
Kuo,
T.C.; Cannon, D.M. Jr.; Feng, W.; Shannon, M.A.; Sweedler, J.V; Bohn, P.W.
“Hybrid Three-Dimensional Nanofluidic/Microfluidic Devices Using Molecular
Gates,” Sens. Actuat. A 2003,
102/3, 223-233.
Cannon, D.M. Jr.; Kuo, T.C.; Sweedler,
J.V.; Shannon, M.A.; Bohn, P.W. “Nanocapillary
Array Interconnects for Gated Analyte Injections and Electrophoretic
Separations in Multilayer Microfluidic Architectures,” Analyt. Chem.2003, 75,
2224-2230.
Angew. Chem. Intl. Ed. Engl. 2004,
43, 1862-1865.
Tulock, J.J.; Shannon, M.A.; Bohn, P.W.; Sweedler, J.V. “Microfluidic Separation and
Gateable Fraction Collection for Mass-Limited Samples,” Analyt. Chem. 2004, 76,
6419-6425.
Swearingen, C.B.; Wernette, D.P.; Cropek,
D.M.; Lu, Y.; Sweedler, J.V.; Bohn, P.W. “Immobilization of a Catalytic DNA
Molecular Beacon on Au for Pb(II) Detection,” Analyt. Chem. 2005, 77,
442-448.
Chang, I.H.; Tulock,J.J.; Liu, J.; Kim, W.S.;
Cannon, D.M. Jr.; Lu, Y.; Bohn, P.W.; Sweedler, J.V.; Cropek, D.M.
“Miniaturized Lead Sensor Based on a Lead Specific Catalytic DNAzyme in a Nanocapillary
Interconnected Microfluidic Device,” Environm.
Sci. Technol., 2005, 39,
3756-3761.
Chatterjee, A.N.; Cannon, D.M Jr.; Gatimu, E.N;
Sweedler, J.V.; Aluru, N.R.; Bohn, P.W. “Modeling and Simulation of Ionic
Currents in Three-Dimensional Microfluidic Devices with Nanofluidic
Interconnects,” J. Nanopart. Res. 2005, 7, 507-16.
Fa, K.; Tulock, J.J.; Sweedler, J.V.; Bohn,
P.W. “Profiling pH Gradients across
Nanocapillary Array Membranes Connecting Microfluidic Channels,” J. Am. Chem. Soc.2005, 127, 13928-13933.
Kirk, J.S.;
Sweedler, J.V.; Bohn, P.W. “Nanofluidic
Injection and Heterogeneous Kinetics of Organomercaptan Adsorption to Colloidal
Gold in a Microfluidic Stream,” Analyt. Chem., 2006, 78, 2335-2341.
Gatimu, E.N.; King, T.L.; Sweedler, J.V.;
Bohn, P.W. “Three-Dimensional
Integrated Microfluidic Architectures Enabled through Electrically Switchable
Nanocapillary Array Membranes,” Biomicrofluidics 2007, 1, 021502(1-11). |