Wei-Ssu Liao

Evaporation-Induced Assembly of Quantum Dots into Nanorings

Herein, we demonstrate the controlled formation of two-dimensional periodic arrays of ring-shaped nanostructures assembled from CdSe semiconductor quantum dots (QDs). The patterns were fabricated by using an evaporative templating method. This involves the introduction of an aqueous solution containing both quantum dots and polystyrene microspheres onto the surface of a planar hydrophilic glass substrate. The quantum dots became confined to the meniscus of the microspheres during evaporation, which drove ring assembly via capillary forces at the polystyrene sphere/glass substrate interface. The geometric parameters for nanoring formation could be controlled by tuning the size of the microspheres and the concentration of the QDs employed. This allowed hexagonal arrays of nanorings to be formed with thicknesses ranging from single dot necklaces to thick multilayer structures over surface areas of many square millimeters. Moreover, the diameter of the ring structures could be simultaneously controlled. A simple model was employed to explain the forces involved in the formation of nanoparticle nanorings.

Subtractive Patterning via Chemical Lift-Off Lithography

Patterning by Subtraction Soft lithographic patterning is usually a “positive” inking process. A polymer stamp is cured on a hard master substrate and then inked with molecules such as alkane thiols, which can then be transferred to a second substrate (such as gold). However, the resolution of the transferred pattern is often degraded by surface diffusion. Liao et al. (p. 1517; see the Perspective by Rogers) obtained higher resolution in a subtractive approach, in which oxygen-plasma–activated silicone stamps removed hydroxyl-terminated alkane thiols from gold surfaces. This lift-off process also removed the terminal gold atom bound to the alkane thiol. The bare regions could be backfilled with protein molecules, and multiple lift-off steps could create patterns with features as small as 40 nanometers. Oxidized silicone-rubber stamps can pattern bare regions on gold surfaces by removing hydroxyl-terminated alkane thiols. Conventional soft-lithography methods involving the transfer of molecular “inks” from polymeric stamps to substrates often encounter micrometer-scale resolution limits due to diffusion of the transferred molecules during printing. We report a “subtractive” stamping process in which silicone rubber stamps, activated by oxygen plasma, selectively remove hydroxyl-terminated alkanethiols from self-assembled monolayers (SAMs) on gold surfaces with high pattern fidelity. The covalent interactions formed at the stamp-substrate interface are sufficiently strong to remove not only alkanethiol molecules but also gold atoms from the substrate. A variety of high-resolution patterned features were fabricated, and stamps were cleaned and reused many times without feature deterioration. The remaining SAM acted as a resist for etching exposed gold features. Monolayer backfilling into the lift-off areas enabled patterned protein capture, and 40-nanometer chemical patterns were achieved.

From the bottom up: dimensional control and characterization in molecular monolayers

Self-assembled monolayers are a unique class of nanostructured materials, with properties determined by their molecular lattice structures, as well as the interfaces with their substrates and environments. As with other nanostructured materials, defects and dimensionality play important roles in the physical, chemical, and biological properties of the monolayers. In this review, we discuss monolayer structures ranging from surfaces (two-dimensional) down to single molecules (zero-dimensional), with a focus on applications of each type of structure, and on techniques that enable characterization of monolayer physical properties down to the single-molecule scale.

Separation and migration behavior of structurally related phenothiazines in cyclodextrin-modified capillary zone electrophoresis

The influences of buffer pH and the concentration of beta-cyclodextrins (beta-CDs) on the separation and migration behavior of 13 structurally related phenothiazines in CD-modified capillary zone electrophoresis (CD-CZE) using a phosphate background electrolyte at low pH were investigated. We focused on the separation of these phenothiazines, including the enantiomers of chiral analytes, with the use of beta-CD and hydroxypropyl-beta-CD (HP-beta-CD) as electrolyte modifiers or chiral selectors at concentrations less than 8 mM. The results indicate that the interactions of phenothiazines with beta-CDs are very strong and that effective separations of 13 analytes can be achieved with addition of 0.3 mM beta-CD or 0.5 mM HP-beta-CD in a phosphate buffer at pH 3.0. Binding constants of phenothiazines to beta-CDs were evaluated for a better understanding of the interactions of phenothiazines with beta-CDs.

Enantioseparation of phenothiazines in cyclodextrin-modified micellar electrokinetic chromatography

In this study, enantioseparations of five phenothiazines in cyclodextrin (CD)-modified micellar electrokinetic chromatography (MEKC) were investigated using a citrate buffer containing tetradecyltrimethylammonium bromide (TTAB) as a cationic surfactant at low pH. Beta-cyclodextrin (beta-CD) and hydroxylpropyl-beta-CD (HP-beta-CD) were selected as chiral selectors. The results indicate that the separation window is greatly enlarged by beta-CD concentration and that the separability and selectivity of phenothiazines are remarkably influenced by the concentrations of both beta-CD and TTAB, as well as buffer pH. The interaction of thioridazine with beta-CDs is considerably reduced in the presence of TTAB micelles due to competitive complexation of thioridazine with TTAB micelles, which is pH-dependent. As a result, effective enantioseparation of thioridazine is simultaneously achievable with that of trimeprazine and promethazine or ethopropazine in MEKC with addition of either beta-CD or HP-beta-CD, respectively, to a micellar citrate buffer containing TTAB at pH 3.5. Better enantioresolution of thioridazine in MEKC than in capillary zone electrophoresis can be obtained.

Benchtop chemistry for the rapid prototyping of label-free biosensors: Transmission localized surface plasmon resonance platforms

Herein, a simple label-free biosensor fabrication method is demonstrated based on transmission localized surface plasmon resonance (T-LSPR). The platform, which consists of a silver nanoparticle array, can be prepared in just a few minutes using benchtop chemistry. The array was made by a templating technique in conjunction with the photoreduction of Ag ions from solution. This metal surface was functionalized with biotin-linked thiol ligands for binding streptavidin molecules from solution. For an array of 19 nm diameter silver nanoparticles, a redshift in the T-LSPR spectrum of 24 nm was observed upon protein-ligand binding at saturation. The binding constant was found to be 2 × 1012 M−1. Platforms were also fabricated with silver nanoparticles of 34, 55, and 72 nm diameters. The maximum LSPR wavelength shift was nanoparticle size dependent and the maximum sensitivity was obtained with the smaller nanoparticles.

Controlled DNA Patterning by Chemical Lift-Off Lithography: Matrix Matters.

Nucleotide arrays require controlled surface densities and minimal nucleotide-substrate interactions to enable highly specific and efficient recognition by corresponding targets. We investigated chemical lift-off lithography with hydroxyl- and oligo(ethylene glycol)-terminated alkanethiol self-assembled monolayers as a means to produce substrates optimized for tethered DNA insertion into post-lift-off regions. Residual alkanethiols in the patterned regions after lift-off lithography enabled the formation of patterned DNA monolayers that favored hybridization with target DNA. Nucleotide densities were tunable by altering surface chemistries and alkanethiol ratios prior to lift-off. Lithography-induced conformational changes in oligo(ethylene glycol)-terminated monolayers hindered nucleotide insertion but could be used to advantage via mixed monolayers or double-lift-off lithography. Compared to thiolated DNA self-assembly alone or with alkanethiol backfilling, preparation of functional nucleotide arrays by chemical lift-off lithography enables superior hybridization efficiency and tunability.

Double-Sided Opportunities Using Chemical Lift-Off Lithography

We discuss the origins, motivation, invention, development, applications, and future of chemical lift-off lithography, in which a specified pattern of a self-assembled monolayer is removed, i.e., lifted off, using a reactive, patterned stamp that is brought into contact with the monolayer. For Au substrates, this process produces a supported, patterned monolayer of Au on the stamp in addition to the negative pattern in the original molecular monolayer. Both the patterned molecular monolayer on the original substrate and the patterned supported metal monolayer on the stamp are useful as materials and for further applications in sensing and other areas. Chemical lift-off lithography effectively lowers the barriers to and costs of high-resolution, large-area nanopatterning. On the patterned monolayer side, features in the single-nanometer range can be produced across large (square millimeter or larger) areas. Patterns smaller than the original stamp feature sizes can be produced by controlling the degree of contact between the stamp and the lifted-off monolayer. We note that this process is different than conventional lift-off processes in lithography in that chemical lift-off lithography removes material, whereas conventional lift-off is a positive-tone patterning method. Chemical lift-off lithography is in some ways similar to microtransfer printing. Chemical lift-off lithography has critical advantages in the preparation of biocapture surfaces because the molecules left behind are exploited to space and to orient functional(ized) molecules. On the supported metal monolayer side, a new two-dimensional material has been produced. The useful important chemical properties of Au (vis-à-vis functionalization with thiols) are retained, but the electronic and optical properties of bulk Au or even Au nanoparticles are not. These metal monolayers do not quench excitation and may be useful in optical measurements, particularly in combination with selective binding due to attached molecular recognition elements. In contrast to materials such as graphene that have bonding confined to two dimensions, these metal monolayers can be straightforwardly patterned-by patterning the stamp, the initial monolayer, or the initial substrate. Well-developed thiol-Au and related chemistries can be used on the supported monolayers. As there is little quenching and photoabsorption, spectroscopic imaging methods can be used on these functionalized materials. We anticipate that the properties of the metal monolayers can be tuned by varying the chemical, physical, and electronic connections made by and to the supporting molecular layers. That is, the amount of charge in the layer can be determined by controlling the density of S-Au (or other) connections and the molecular backbone and functionality, which determine the strength with which the chemical contact withdraws charge from the metal. This process should work for other coinage-metal substrates and additional systems where the binding of the outermost layers to the substrate is weaker than the molecule-substrate attachment.

Thin Gold Film-Assisted Fluorescence Spectroscopy for Biomolecule Sensing

We present a configuration for fluorescence spectroscopy that exploits the optical properties of semitransparent gold films and widely available instrumentation. This method enables monitoring of biomolecule interactions with small molecules tethered on substrates in multicomponent environments. The neurotransmitter serotonin (5-hydroxytryptamine) was covalently attached to self-assembled monolayers on thin gold films at low density to facilitate antibody recognition. Protein-binding studies were performed in a fluorescently labeled immunoassay format. We find that the use of this method enables evaluation of nonspecific binding and relative quantification of specific binding between competing binding partners. This fluorescence spectroscopy technique has the potential to assess biosensor or medical device responses in complex biological matrices.

Multicolor Functional Carbon Dots via One-Step Refluxing Synthesis

Carbon dots are admirable fluorescent nanomaterials due to their low cost, high photostability, excellent biocompatibility, and environmental friendliness. Most conventional carbon dot fabrication approaches produce single-colored fluorescent material in the preparation process; different methods are therefore required to synthesize distinct carbon dots for specific optical applications. In this study, carbon dots carrying different emission colors are prepared through a one-step refluxing process. The emission of these materials can be well-tuned by sodium hydroxide content in the precursor solution. The carbon dots produced are used as sensing probes based on the spectrofluorometric inner filter effect for target molecule detection. Three sensing categories that combine carbon dots and inner filter effect are demonstrated, including direct, metal nanoparticle-assisted, and enzymatic reaction-supported detection. Caffeine, melamine, and fenitrothion are selected as targets to demonstrate the strategies, respectively. These multifunctional carbon dot-based sensors achieve comparable sensitivity toward analytes with a much more convenient preparation route.