The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

Fundamental Principles Laminar Boundary Layer Flow Laminar Duct Flow External Natural Convection Internal Natural Convection Transition to Turbulence Turbulent Boundary Layer Flow Turbulent Duct Flow Free Turbulent Flows Convection with Change of Phase Mass Transfer Convection in Porous Media.

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Convection Heat Transfer

This thesis explores transport phenomena in nanochannels on a chip. Fundamental nanofluidic ionic studies form the basis for novel separation and preconcentration applications for proteomic purposes. The measurements were performed with 50-nm-high 1D nanochannels, which are easily accessible from both sides by two microchannels. Nanometer characteristic apertures were manufactured in the bonded structure of Pyrex-amorphous silicon – Pyrex, in which the thickness of the amorphous silicon layer serves as a spacer to define the height of the nanochannels. The geometry of the nanometer-sized apertures is well defined, which simplifies the modeling of the transport across them. Compared to biological pores, the present nanochannels in Pyrex offer increased stability. Fundamental characteristics of nanometer-sized apertures were obtained by impedance spectroscopy measurements of the nanochannel at different ionic strengths and pH values. A conductance plateau (on a log-log scale) was modeled and measured, establishing due to the dominance of the surface charge density in the nanochannels, which induces an excess of mobile counterions to maintain electroneutrality. The nanochannel conductance can be regulated at low ionic strengths by pH adjustment, and by an external voltage applied on the chip to change the zeta potential. This field-effect allows the regulation of ionic flow which can be exploited for the fabrication of nanofluidic devices. Fluorescence measurements confirm that 50-nm-high nanochannels show an exclusion of co-ions and an enrichment of counterions at low ionic strengths. This permselectivity is related to the increasing thickness of the electrical double layer (EDL) with decreasing salt concentrations, which results in an EDL overlap in an aperture if the height of the nanochannel and the thickness of the EDL are comparable in size. The diffusive transport of charged species and therefore the exclusion-enrichment effect was described with a simple model based on the Poisson-Boltzmann equation. The negatively charged Pyrex surface of the nanometer characteristic apertures can be inversed with chemical surface pretreatments, resulting in an exclusion of cations and an enrichment of anions. When a pressure gradient is applied across the nanochannels, charged molecules are electrostatically rejected at the entrance of the nanometer-sized apertures, which can be used for separation processes. Proteomic applications are presented such as the separation and preconcentration of proteins. The diffusion of Lectin proteins with different isoelectric points and very similar compositions were controlled by regulating the pH value of the buffer. When the proteins are neutral at their pI value, the diffusion coefficient is maximal because the biomolecules does not interact electrostatically with the charged surfaces of the nanochannel. This led to a fast separation of three Lectin proteins across the nanochannel. The pI values measured in this experiment are slightly shifted compared to the values obtained with isoelectric focusing because of reversible adsorption of proteins on the walls which affects the pH value in the nanochannel. An important application in the proteomic field is the preconcentration of biomolecules. By applying an electric field across the nanochannel, anionic and cationic analytes were preconcentrated on the cathodic side of the nanometer-sized aperture whereas on the anodic side depletion of ions was observed. This is due to concentration polarization, a complex of effects related to the formation of ionic concentration gradients in the electrolyte solution adjacent to an ion-selective interface. It was measured that the preconcentration factor increased with the net charge of the molecule, leading to a preconcentration factor of > 600 for rGFP proteins in 9 minutes. Such preconcentrations are important in micro total analysis systems to achieve increased detection signals of analytes contained in dilute solutions. Compared to cylindrical pores, our fabrication process allows the realization of nanochannels on a chip in which the exclusion-enrichment effect and a big flux across the nanometer-sized aperture can be achieved, showing the interest for possible micro total analysis system applications. The described exclusion-enrichment effect as well as concentration polarization play an important role in transport phenomena in nanofluidics. The appendix includes preliminary investigations in DNA molecule separation and fluorescence correlation spectroscopy measurements, which allows investigating the behavior of molecules in the nanochannel itself.

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Transport phenomena in nanofluidics

Numerical Initial Value Problems in Ordinary Differential Equations

Polymer nanoparticles: Preparation techniques and size-control parameters

The hydrodynamics of cocurrent gas-liquid flow in packed beds is analyzed by extending the concept of relative permeability to the inertial regime.

The relative permeabilities of the gas and liquid phases are functions of the saturation of the liquid phase. These functions are found from an analysis of experimental data. The relations obtained are used to develop empirical correlations for predicting liquid holdup and pressure drop in gas-liquid cocurrent downflow in packed beds over a wide range of operating conditions. The correlations proposed give very good results when compared to experimental data yielding, in general, mean relative deviations lower than existing correlations. In addition, a new equation is proposed for predicting static holdup in packed beds which is based on a more physically realistic characteristic length than that used in previous studies.

hydrodynamic parameters for gas-liquid cocurrent flow in packed beds

Longitudinal and lateral dispersion coefficients were measured at various axial positions in a packed bed in the Peclet number range from 102 to 104. Three different types of packings were used: uniform size particles, a narrow size distribution, and a wide size distribution. For the case of uniform particles the longitudinal dispersivities were found to be strong functions of position in the bed unless the dispersion length satisfies a constraint dependent on the value of the Peclet number. Generally, the larger the Peclet number, the larger the required length for constant axial dispersivities to be achieved. For the case of the wide size distribution, longitudinal dispersivities were larger than in the uniform particle case, and they required a longer dispersion length to achieve a constant value. This suggests a characteristic length for dispersion larger than the mean hydraulic radius. The lateral dispersivities were found to be insensitive to the distribution of particle sizes or location in the bed.

Longitudinal and lateral dispersion in packed beds: Effect of column length and particle size distribution

In cocurrent downflow of a gas and a liquid through a packed column, a transition from trickling flow to pulsing flow is observed as one increases the flow rates. A simple macroscopic model for the two-phase flow is analyzed to examine whether this regime transition should be viewed as the loss of stability of a steady state or the loss of existence of any solution for the steady-state equations of motion. The former appears to be a more reasonable interpretation and an explicit algebraic criterion for the onset of pulsing is presented.

Onset of pulsing in two‐phase cocurrent downflow through a packed bed

A family of linear hexapeptides composed of histidine on the N-terminus followed by aromatic amino acid(s) and positively charged amino acid(s) has been identified through a three-step screening of a synthetic solid phase library. These peptides were able to recognize human immunoglobulin G (HIgG) through its Fc region, and their selectivity to Fc is comparable to Protein A. This is the first known report of short peptides that are able to bind HIgG by recognizing its Fc portion. One of the ligands from the identified family, HWRGWV, was examined for its ability to isolate HIgG from complex mixtures. It was found that HWRGWV possessed the potential to purify HIgG from complete mammalian cell culture medium containing 10% fetal calf serum with purity comparable to commercially available resins, but using milder elution conditions. HWRGWV bound all HIgG subclasses and IgGs from bovine, mouse, goat, and rabbit. The broad affinity spectrum as well as its Fc recognition ability may be useful in capturing and detecting both polyclonal and monoclonal antibodies.

Ruben G. Carbonell

Papers

hydrodynamic parameters for gas-liquid cocurrent flow in packed beds

Longitudinal and lateral dispersion in packed beds: Effect of column length and particle size distribution

Onset of pulsing in two‐phase cocurrent downflow through a packed bed

Hexamer peptide affinity resins that bind the Fc region of human immunoglobulin G

Purification of human immunoglobulin G via Fc-specific small peptide ligand affinity chromatography.