Lane A. Baker

Preparation and characterization of dendrimer-gold colloid nanocomposites.

Au colloids in the 2-3-nm size regime were prepared by in situ reduction of HAuCl(4) in the presence of poly(amidoamine) dendrimers. The dendrimers encapsulate the colloids, imparting stability to the aqueous colloidal solutions. The nanocomposite materials can be isolated by precipitation. The dendrimer generation used in the synthesis controls the size of the resultant colloids:  lower-generation dendrimers give rise to larger colloids. The materials were characterized by infrared and UV-vis spectroscopy and transmission electron microscopy.

Scanning Ion Conductance Microscopy

Scanning ion conductance microscopy (SICM) is a versatile type of scanning probe microscopy for studies in molecular biology and materials science. Recent advances in feedback and probe fabrication have greatly increased the resolution, stability, and speed of imaging. Noncontact imaging and the ability to deliver materials to localized areas have made SICM especially fruitful for studies of molecular biology, and many examples of such use have been reported. In this review, we highlight new developments in the operation of SICM and describe some of the most exciting recent studies from this growing field.

Z-SCAN MEASUREMENT OF THE NONLINEAR ABSORPTION OF A THIN GOLD FILM

We have used the z-scan technique at a wavelength (532 nm) near the transmission window of bulk gold to measure the nonlinear absorption coefficient of continuous approximately 50-A-thick gold films, deposited onto surface-modified quartz substrates. For highly absorbing media such as metals, we demonstrate that determination of either the real or imaginary part of the third-order susceptibility requires a measurement of both nonlinear absorption and nonlinear refraction, i.e., both open- and closed-aperture z scans must be performed. Closed-aperture z scans did not yield a sufficient signal for the determination of the nonlinear refraction. However, open-aperture z scans yielded values ranging from β=1.9×10−3 to 5.3×10−3 cm/W in good agreement with predictions which ascribe the nonlinear response to a Fermi smearing mechanism. We note that the sign of the nonlinearity is reversed from that of gold nanoparticle composites, in accordance with the predictions of mean field theories.

Fundamental Studies of Nanofluidics: Nanopores, Nanochannels,and Nanopipets

Ion, particle, and fluid transport in nanofluidic devices has received considerable attention over the past two decades due to unique transport properties exhibited at the nanoscale.1,2 Phenomena such as double layer overlap, high surface-to-volume ratios, surface charge, ion-current rectification, and entropic barriers can influence transport in and around nanofluidic structures because the length scales of these forces and the critical dimensions of the device are similar. Advances in micro- and nanofabrication techniques provide the ability to design a variety of well-defined nanofluidic geometries to study these phenomena and their effects on ion and fluid transport. Integration of micro- and nanofluidic structures into lab-on-a-chip devices permits increased functionality that is useful for a range of analytical applications.3,4 This Review focuses on recent advances in nanofabrication techniques as well as studies of fundamental transport in nanofluidic devices. Nanopores, nanochannels, and nanopipets are three common nanofluidic structures that have been influential in studying nanofluidic transport. Because of space limitations, we have limited the scope of this Review to studies with these three structures, and we focus our attention primarily on work published between January 2011 and August 2014. We do not discuss work with carbon nanotubes,5 nanomeshes,6 or nanowires.7 Figure ​Figure11 shows examples of the three nanofluidic geometries discussed here. Nanopores are typically formed perpendicular to the plane of a substrate and are characterized by a critical limiting dimension, which is measured by scanning electron microscopy (SEM), transmission electron microscopy (TEM), or conductance measurements. Pores are fabricated in a variety of materials, e.g., poly(carbonate), poly(ethylene terephthalate), or silicon nitride, and can have an asymmetric (Figure ​(Figure1a)1a) or symmetric (Figure ​(Figure1b)1b) shape, depending on the fabrication technique. Symmetric pores are either cylindrically shaped with a constant critical dimension determined by electron microscopy or hourglass-shaped with a critical dimension at the center of the pore. Although electron microscopy is capable of measuring exterior pore dimensions, the exact inner geometry is often unknown and may contain an asymmetry between two symmetric features, e.g., cigar-shaped pores. Asymmetric nanopores typically have a narrow tip and a wide base with a funnel-shaped geometry along the pore axis. Tip and base dimensions are measured by SEM, but the exact pore geometry is often unknown. Nanochannels often refer to in-plane structures with either symmetric (Figure ​(Figure1c)1c) or asymmetric (Figure ​(Figure1d)1d) geometries. Channels may be confined to the nanoscale in depth, width, or both, depending on the fabrication method. Nanochannels are commonly fabricated in glass and polymer substrates and characterized by SEM and atomic force microscopy (AFM). The in-plane nature of these channels allows the integration of well-defined features into more complex geometries, and any two-dimensional (2D) channel architecture can be designed. Nanopipets are specialized nanopores fabricated from pulled glass or fused-silica capillaries (Figure ​(Figure1e,f). The1e,f). The geometry of a nanopipet is conically shaped with a critical tip diameter of tens to hundreds of nanometers, which can be measured by electron microscopy. Unlike nanopores and nanochannels, nanopipets can be easily coupled with position control, which allows the tip of the nanopipets to be positioned in specific locations or used in scanned probe microscopies. Figure 1 Nanopores, nanochannels, and nanopipets are three common nanofluidic platforms. Nanopores are typically out-of-plane structures and have either an asymmetric or symmetric geometry. Conical nanopores have a wide base as shown in panel a that tapers to ...

Applications of nanopipettes in the analytical sciences

In this review, we describe measurements and applications of interest to the analytical community that makes use of simple nanopipettes. Fabricated by applying heat during the separation of a glass capillary, nanopipettes provide a route for nanoscale studies of ion transport and for development of chemical and biochemical sensors. When mounted on a translation stage, nanopipettes also enable unique modes of imaging and material deposition. These facets of nanopipette research, as well as some of the unique properties of nanopipettes, will be discussed.

Rectification of Ion Current in Nanopipettes by External Substrates

We describe ion distribution and the current-voltage (i-V) response of nanopipettes at different probe-to-substrate distances (Dps) as simulated by finite-element methods. Results suggest electrostatic interactions between a charged substrate and the nanopipette dominate electrophoretic ion transport through the nanopipette when Dps is within 1 order of magnitude of the Debye length (∼10 nm for a 1 mM solution as employed in the simulation). Ion current rectification (ICR) and permselectivity associated with a neutral or charged nanopipette can be reversibly enhanced or reduced dependent on Dps, charge polarity, and charge density (σ) of the substrate. Regulation of nanopipette current is a consequence of the enrichment or depletion of ions within the nanopipette interior, which influences conductivity of the nanopipette. When the external substrate is less negatively charged than the nanopipette, the substrate first reduces, and then enhances the ICR as Dps decreases. Surprisingly, both experimental and simulated data show that a neutral substrate was also able to reduce and reverse the ICR of a slightly negatively charged nanopipette. Simulated results ascribe such effects to the elimination of ion depletion within the nanopipette at positive potentials.

Biomaterials and Biotechnologies Based on Nanotube Membranes

In this review, we consider materials and systems based on nanotubes formed within the pores of synthetic nanoporous membranes. The topics considered are of potential interest in the fields of biomaterials or biotechnology. There are three general membrane-based strategies that have been used to prepare materials: In the first strategy, template synthesis, nanometer scale pores are used to synthesize and modify materials. In the second strategy, we describe steps toward the design of nanotube-based membrane sensors. In the third approach, nanometer scale pores are used to separate species that translocate the membrane. In this review we consider the materials and techniques used to create, manipulate, and interrogate these bio-oriented nanotube membrane systems.

Conical nanopore membranes: solvent shaping of nanopores

We have undertaken a systematic investigation of the influence of ethanol on the shape of conical pores produced by the track-etch technique in poly(ethylene terephthalate) films. We have found that the cone angle of the conical nanopore generated is dependent on the amount of ethanol present in an alkaline etching solution. By varying the percentage of ethanol in the etch solution, precise control over the geometry of the conical nanopore and nanomaterials templated within these pores can be attained. We prove this by plating gold nanocones within the various conical nanopores prepared, dissolving the membrane to liberate the nanocones, and imaging the nanocones using scanning electron microscopy. The results of these investigations are reported here.

Measurement of ion currents through porous membranes with scanning ion conductance microscopy.

Scanning ion conductance microscopy (SICM) was used to interrogate ion currents emanating from nanometer-scale pores of a polymer membrane. The transport activity of individual pores was measured by examining ion current images and corresponding topographic images recorded simultaneously. Localized ion currents over individual nanopores were generated by introducing a concentration difference between the upper and lower chambers of a diffusion cell. To better estimate these localized ion currents, Goldman-Hodgkin-Katz (GHK) theory was used to model ion current through a permeable membrane under gradients of both concentration and applied potential. Experimental ion current profiles over a single pore fit well with theoretical plots calculated from the GHK model. On the basis of this analysis, nanoscale transport properties can be measured with SICM.

Dendrimer-Mediated Adhesion between Vapor-Deposited Au and Glass or Si Wafers.

Here, we report the use of amine-terminated poly(amidoamine) (PAMAM) dendrimers as adhesion promoters between vapor-deposited Au films and Si-based substrates. This method is relatively simple, requiring only substrate cleaning, dipping, and rinsing. Proof of concept is illustrated by coating glass slides and single-crystal Si wafers with monolayers of PAMAM dendrimers and then evaporating adherent, 150-nm-thick Au films atop the dendritic adhesion promoter. Scanning tunneling microscopy and cyclic voltammetry have been used to assess the surface roughness and electrochemical stability of the Au films. The effectiveness of the dendrimer adhesion layer is demonstrated using standard adhesive-tape peel tests.