Chemistry, Department of

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Simultaneous Patterning of Two Different Types of Nanoparticles into Alternating Domains of a Striped Array of a Polymer Blend in a Single Spin-Casting Step

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2014-11-01
Abstract: 

A fast and convenient method is developed for simultaneously patterning inorganic nanoparticles with different optical, electronic or magnetic functionality to specific surface regions, by spin-casting onto microcontact printed substrates blend solutions in which the two nanoparticle types are functionalized with surface polymer brush layers of different surface energies. The process is based on phase separation of different nanoparticles based on their immiscible brush layers during spin-casting, with the underlying surface energy heterogeneity of the patterned substrate directing the different NP types to domains of different surface energies. Here, we specifically demonstrate the simultaneous localization of cadmium sulfide quantum dots (CdS QDs), addressed with a surface layer of polystyrene (PS), and silver nanoparticles (Ag NPs), addressed with a surface layer of poly(methyl methacrylate) (PMMA), onto the non-polar and polar surface domains, respectively, of hydrophilic glass patterned with hydrophobic octadecyltrichlorosilane (OTS) stripe arrays with micron-scale periodicities. In order to prevent gelation of solvent-swollen polymer-brush coated NPs during spin casting, which effects strong kinetic constraints on phase separation and localization, PS, PMMA or PS/PMMA homopolymer blends of sufficiently high Mw were added to the NP blends to increase the free volume between approaching NPs. The process parameters were fine-tuned to obtain control over defects in the obtained patterns.

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A Proposed Mechanism of the Influence of Gold Nanoparticles on DNA Hybridization

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2014-06-25
Abstract: 

A combination of gold nanoparticles (AuNPs) and nucleic acids has been used in biosensing applications. However, there is a poor fundamental understanding of how gold nanoparticle surfaces influence the DNA hybridization process. Here, we measured the rate constants of the hybridization and dehybridization of DNA on gold nanoparticle surfaces to enable the determination of activation parameters using transition state theory. We show that the target bases need to be detached from the gold nanoparticle surfaces before zipping. This causes a shift of the rate-limiting step of hybridization to the mismatch-sensitive zipping step. Furthermore, our results propose that the binding of gold nanoparticles to the single-stranded DNA segments (commonly known as bubbles) in the duplex DNA stabilizes the bubbles and accelerates the dehybridization process. We employ the proposed mechanism of DNA hybridization/dehybridization to explain the ability of 5 nm diameter gold nanoparticles to help discriminate between single base-pair mismatched DNA molecules when performed in a NanoBioArray chip. The mechanistic insight into the DNA–gold nanoparticle hybridization/dehybridization process should lead to the development of new biosensors.

A combination of gold nanoparticles (AuNPs) and nucleic acids has been used in biosensing applications. However, there is a poor fundamental understanding of how gold nanoparticle surfaces influence the DNA hybridization process. Here, we measured the rate constants of the hybridization and dehybridization of DNA on gold nanoparticle surfaces to enable the determination of activation parameters using transition state theory. We show that the target bases need to be detached from the gold nanoparticle surfaces before zipping. This causes a shift of the rate-limiting step of hybridization to the mismatch-sensitive zipping step. Furthermore, our results propose that the binding of gold nanoparticles to the single-stranded DNA segments (commonly known as bubbles) in the duplex DNA stabilizes the bubbles and accelerates the dehybridization process. We employ the proposed mechanism of DNA hybridization/dehybridization to explain the ability of 5 nm diameter gold nanoparticles to help discriminate between single base-pair mismatched DNA molecules when performed in a NanoBioArray chip. The mechanistic insight into the DNA–gold nanoparticle hybridization/dehybridization process should lead to the development of new biosensors.

Document type: 
Article
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Electrochemically Active Nickel Foams as Support Materials for Nanoscopic Platinum Electrocatalysts

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2014-06-27
Abstract: 

Platinum is deposited on open-cell nickel foam in low loading amounts via chemical reduction of Pt cations (specifically, Pt2+ or Pt4+) originating from aqueous Pt salt solutions. The resulting Pt-modified nickel foams (Pt/Ni foams) are characterized using complementary electrochemical and materials analysis techniques. These include electron microscopy to examine the morphology of the deposited material, cyclic voltammetry to evaluate the electrochemical surface area of the deposited Pt, and inductively coupled plasma optical emission spectrometry to determine the mass of deposited Pt on the Ni foam substrate. The effect of potential cycling in alkaline media on the electrochemical behavior of the material and the stability of Pt deposit is studied. In the second part of this paper, the Pt/Ni foams are applied as electrode materials for hydrogen evolution, hydrogen reduction, oxygen reduction, and oxygen evolution reactions in an aqueous alkaline electrolyte. The electrocatalytic activity of the electrodes toward these processes is evaluated using linear sweep voltammetry curves and Tafel plots. The results of these studies demonstrate that nickel foams are acceptable support materials for nanoscopic Pt electrocatalysts and that the resulting Pt/Ni foams are excellent electrocatalysts for the hydrogen evolution reaction. An unmodified Ni foam is shown to be a highly active electrode for the oxygen evolution reaction.

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Article
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Ordered Porous Gold Electrodes to Enhance the Sensitivity of Enzyme-Based Glucose Sensors

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2013-12-27
Abstract: 

Glucose sensors are essential tools for diabetes patients to use in monitoring their blood glucose levels. However, to be able to detect glucose in non-invasively collected physiological fluids, such as tears and urine, the sensitivity of these glucose sensors must be significantly higher than sensors that are currently used to detect glucose concentrations in blood. Increasing the specific surface area of enzyme-based glucose sensors through the use of ordered porous gold electrodes has been shown to enhance the sensitivity of these sensors. The enzyme-based ordered porous gold glucose sensor was demonstrated to be suitable in detecting glucose concentrations ranges that are similar to those occurring in tears. Although sensitivity of the glucose sensor is enhanced, the saturation threshold of the sensor is lowered. Further optimizations of the porous gold electrodes are required to eliminate signal saturation of these improved sensors.

Document type: 
Article
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Platinum Ordered Porous Electrodes: Developing a Platform for Fundamental Electrochemical Characterization

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2013-07-09
Abstract: 

High surface area platinum electrodes with an ordered porous structure (Pt-OP electrodes) have been prepared and characterized by electrochemical methods. This study builds a foundation upon which we can seek an in-depth understanding of the limitations and design considerations to make efficient and stable Pt-OP electrodes for use in electrochemical applications. A set of Pt-OP electrodes were prepared by controlled electrodeposition of Pt through a self-assembled array of spherical particles and subsequent removal of the spherical templates by solvent extraction. The preparation method was shown to be reproducible and the resulting electrodes were found to have clean Pt surfaces and a large electrochemical surface area (A ecsa) resulting from both the porous structure, as well as the nano- and micro-scale surface roughness. Additionally, the Pt-OP electrodes exhibit a surface area enhancement comparable to commercially available electrocatalysts. In summary, the Pt-OP electrodes prepared herein show properties of interest for both gaining fundamental insights into electrocatalytic processes and for use in applications that would benefit from enhanced electrochemical response.

Document type: 
Article
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Surface-Initiated Atom Transfer Radical Polymerization Induced Transformation of Selenium Nanowires into Copper Selenide@Polystyrene Core-Shell Nanowires

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2013-09-02
Abstract: 

This Article reports the first preparation of cuprous and cupric selenide nanowires coated with a ∼5 nm thick sheath of polystyrene (copper selenide@polystyrene). These hybrid nanostructures are prepared by the transformation of selenium nanowires in a one-pot reaction, which is performed under ambient conditions. The composition, purity, and crystallinity of the copper selenide@polystyrene products were assessed by scanning transmission electron microscopy, electron energy-loss spectroscopy, X-ray powder diffraction, and X-ray photoelectron spectroscopy techniques. We determined that the single crystalline selenium nanowires are converted into polycrystalline copper selenide@polystyrene nanowires containing both cuprous selenide and cupric selenide. The product is purified through the selective removal of residual, non-transformed selenium nanowires by performing thermal evaporation below the decomposition temperature of these copper selenides. Powder X-ray diffraction of the purified copper selenide nanowires@polystyrene identified the presence of hexagonal, cubic, and orthorhombic phases of copper selenide. These purified cuprous and cupric selenide@polystyrene nanowires have an indirect bandgap of 1.44 eV, as determined by UV–vis absorption spectroscopy. This new synthesis of polymer-encapsulated nanoscale materials may provide a method for preparing other complex hybrid nanostructures.

Document type: 
Article
File(s): 

Platinum Ordered Porous Electrodes: Developing a Platform for Fundamental Electrochemical Characterization

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2013-07-09
Abstract: 

High surface area platinum electrodes with an ordered porous  structure (Pt-OP electrodes) have been prepared and characterized by  electrochemical methods. This study builds a foundation upon which we can  seek an in-depth understanding of the limitations and design considerations  to make efficient and stable Pt-OP electrodes for use in electrochemical  applications. A set of Pt-OP electrodes were prepared by controlled  electrodeposition of Pt through a self-assembled array of spherical particles  and subsequent removal of the spherical templates by solvent extraction. The  preparation method was shown to be reproducible and the resulting electrodes  were found to have clean Pt surfaces and a large electrochemical surface area  (A ecsa) resulting from both the porous structure, as well as the nano- and  micro-scale surface roughness. Additionally, the Pt-OP electrodes exhibit a  surface area enhancement comparable to commercially available  electrocatalysts. In summary, the Pt-OP electrodes prepared herein show  properties of interest for both gaining fundamental insights into  electrocatalytic processes and for use in applications that would benefit  from enhanced electrochemical response. 

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Article
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Optically Active Nanoparticle Coated Polystyrene Spheres

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2013-05-13
Abstract: 

Nanoparticles (NPs) with either plasmonic or upconverting properties have been selectively coated onto the surfaces of polystyrene (PS) spheres, imparting their optical properties to the PS colloids. These NP coated PS spheres have many potential applications, such as in medicine as drug-delivery systems or diagnostic tools. To prepare the NP coated PS spheres, gold or core-shell NaYF4Tm0.5Yb30/NaYF4 NPs were synthesized and separately combined with amino-functionalized PS spheres. The mechanism by which the NPs adhered to the PS spheres is attributed to interactions of the NP and a polyvinylpyrrolidone additive with the surfaces of the PS spheres. Two-photon fluorescence microscopy and SERS analysis demonstrate the potential applications of these NP coated PS spheres.

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Article
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A Tunable Loading of Single-Stranded DNA on Gold Nanorods through the Displacement of Polyvinylpyrrolidone

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2013-09-09
Abstract: 

A quantitative and tunable loading of single-stranded (ss-DNA) molecules onto gold nanorods was achieved through a new method of surfactant exchange. This new method involves the exchange of cetyltrimethylammonium bromide surfactants for an intermediate stabilizing layer of polyvinylpyrrolidone and sodium dodecylsulfate. The intermediate layer of surfactants on the anisotropic gold particles was easily displaced by thiolated ss-DNA, forming a tunable density of single-stranded DNA molecules on the surfaces of the gold nanorods. The success of this ligand exchange process was monitored in part through the combination of extinction, X-ray photoelectron, and infrared absorption spectroscopies. The number of ss-DNA molecules per nanorod for nanorods with a high density of ss-DNA molecules was quantified through a combination of fluorescence measurements and elemental analysis, and the functionality of the nanorods capped with dense monolayers of DNA was assessed using a hybridization assay. Core–satellite assemblies were successfully prepared from spherical particles containing a probe DNA molecule and a nanorod core capped with complementary ss-DNA molecules. The methods demonstrated herein for quantitatively fine tuning and maximizing, or otherwise optimizing, the loading of ss-DNA in monolayers on gold nanorods could be a useful methodology for decorating gold nanoparticles with multiple types of biofunctional molecules.

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Article
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Measuring Shear-Induced Adhesion of Gecko-Inspired Fibrillar Arrays Using Scanning Probe Techniques

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2013-07-30
Abstract: 

The natural ability of geckos and spiders to climb almost all surfaces using the compliant, nano‐structured components on their feet provides motivation for making bio‐inspired adhesives. The goal of the studies in this paper is to create an analytical technique for improving the ability to characterize dry adhesives modeled after these biological systems. The technique described herein uses a scanning probe microscope to manipulate a flat test surface in contact with biomimetic fibrillar arrays while monitoring the adhesion forces. Adhesion forces were measured after both normal contact and shear‐induced contact between the nano‐structured fibrils and the test surface. Results confirm that the adhesion forces are higher for bio‐inspired adhesives after a shear‐induced contact. Variations in these forces can be measured across the sample with micrometer‐scale lateral resolution. This method of analysis can be extended to evaluate bio‐inspired dry adhesives with realistic mechanisms of attachment utilized in robotic and similar applications of these materials.

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