Hydrogel-Based Glucose Sensors: Effects of Phenylboronic Acid Chemical Structure on Response

Phenylboronic acids (PBAs) are being considered for glucose sensing and controlled insulin release, because of their affinity for diol-containing molecules. The interaction of immobilized PBAs in a hydrogel matrix with glucose can lead to volumetric changes that have been used to monitor glucose concentration and release insulin. Although the interaction of PBAs with diol-containing molecules has been intensively studied, the response of PBA-modified hydrogels as a function of the specific PBA chemistry is not well understood. To understand the interaction of immobilized PBAs with glucose in hydrogel systems under physiological conditions, the glucose-dependent volumetric changes of a series of hydrogel sensors functionalized with different classes of PBAs were investigated. The volume change induced by PBA-glucose interactions is converted to the diffracted wavelength shift by a crystalline colloidal array embedded in the hydrogel matrix. The PBAs studied contain varying structural parameters such as the position of the boronic acid on the phenyl ring, different substituents on PBAs and different linkers to the hydrogel backbone. The volumetric change of the PBA modified hydrogels is found to be highly dependent on the chemical structure of the immobilized PBAs. The PBAs that appear to provide linear volumetric responses to glucose are found to also have slow response kinetics and significant hysteresis, while PBAs that show nonlinear responses have fast response kinetics and small hysteresis. Electron-withdrawing substituents, which reduce the p<i>K</i>_a of PBAs, either increase or decrease the magnitude of response, depending on the exact chemical structure. The response rate is increased by PBAs with electron-withdrawing substituents. Addition of a methylene bridge between the PBA and hydrogel backbone leads to a significant decrease in the response magnitude. PBAs with specific desirable features can be selected from the pool of available PBAs and other PBA derivatives with desired properties can be designed according to the findings reported here

Polymer Brushes Patterned with Micrometer-Scale Chemical Gradients Using Laminar Co-Flow

We present a facile microfluidic method for forming narrow chemical gradients in polymer brushes. Co-flow of an alkylating agent solution and a neat solvent in a microfluidic channel forms a diffusion-driven concentration gradient, and thus a gradient in reaction rate at the interface of the two flows, leading to a quaternization gradient in the underlying poly­(2-(dimethylamino)­ethyl methacrylate) polymer brush. The spatial distribution of the quaternized polymer brush is characterized by confocal Raman microscopy. The quaternization gradient length in the polymer brush can be varied with the injection flow rate and the distance from the co-flow junction. A chemical gradient in the polymer brush as narrow as 5 μm was created by controlling these parameters. The chemical gradient by laminar co-flow is compared with numerical calculations that include only one adjustable parameter: the reaction rate constant of the polymer brush quaternization. The calculated chemical gradient agrees with the experimental data, which validates the numerical procedures established in this study. Flow of multiple laminar streams of reactive agent solutions enables single-run fabrication of brush gradients with more than one chemical property. As one example, four laminar streamsneat solvent/benzyl bromide solution/propargyl bromide solution/neat solventgenerate multistep gradients of aromatic and alkyne groups. Because the alkyne functional group is a click-reaction available site, the alkyne gradient could allow small gradient formation with a wide variety of chemical properties in a polymer brush

Molecular Tailoring of Interfacial Failure

Self-assembled monolayers (SAMs) provide an enabling platform for molecular tailoring of the chemical and physical properties of an interface. In this work, we systematically vary SAM end-group functionality and quantify the corresponding effect on interfacial failure between a transfer printed gold (Au) film and a fused silica substrate. SAMs with four different end groups are investigated: 11-amino-undecyltriethoxysilane (ATES), dodecyltriethoxysilane (DTES), 11-bromo-undecyltrimethoxysilane (BrUTMS), and 11-mercapto-undecyltrimethoxysilane (MUTMS). In addition to these four end groups, mixed monolayers of increasing molar ratio of MUTMS to DTES in solution are investigated. The failure of each SAM-mediated interface is initiated by a noncontact laser-induced spallation method at strain rates in excess of 10⁶ s^–1. By making multiple measurements at increasing stress amplitudes (controlled by the laser fluence), we measure interface strengths of 19 ± 1.7, 20 ± 1.3, 52 ± 5.4, and 80 ± 6.5 MPa for interfaces functionalized with ATES, DTES, BrUTMS, and MUTMS, respectively. The interface strength is effectively tuned between the low strength of DTES and the high strength of MUTMS by controlling the concentration of MUTMS in solution. X-ray photoelectron spectroscopy of the failed interfaces reveals the influence of end group functionality on molecular dissociation, which significantly alters the failure process

Tunable Visibly Transparent Optics Derived from Porous Silicon

Visibly transparent porous silicon dioxide (PSiO₂) and PSiO₂/titanium dioxide (TiO₂) optical elements were fabricated by thermal oxidation, or a combination of thermal oxidation and atomic layer deposition infilling, of an electrochemically etched porous silicon (PSi) structure containing an electrochemically defined porosity profile. The thermally oxidized PSiO₂ structures are transparent at visible wavelengths and can be designed to have refractive indices ranging from 1.1 to 1.4. The refractive index can be increased above 2.0 through TiO₂ infilling of the pores. Applying this oxidation and TiO₂ infilling methodology enabled tuning of a distributed Bragg reflector (DBR) formed from PSi across the visible spectrum. At the maximum filling, the DBR exhibited a transmission of 2% at 620 nm. Simulations match well with measured spectra. In addition to forming DBR filters, phase-shaping gradient refractive index (GRIN) elements were formed. As a demonstration, a 4 mm diameter radial GRIN PSiO₂ element with a parabolic, lens-like phase profile with a calculated focal length of 1.48 m was formed. The calculated focal length was reduced to 0.80 m upon the addition of TiO₂. All the structures showed broad transparency in the visible and were stable to the materials conversion process

Low-Temperature Hydrothermal Synthesis of Colloidal Crystal Templated Nanostructured Single-Crystalline ZnO

Single crystal semiconductors almost always exhibit better optoelectrical properties than their polycrystalline or amorphous counterparts. While three-dimensionally (3D) nanostructured semiconductor devices have been proposed for numerous applications, in the vast majority of reports, the semiconductor is polycrystalline or amorphous, greatly reducing the potential for advanced properties. While technologies for 3D structuring of semiconductors via use of a 3D template have advanced significantly, approaches for epitaxially growing nanostructured single crystal semiconductors within a template remain limited. Here, we demonstrate the epitaxial growth of 3D-structured ZnO through colloidal templates formed from 225 and 600 nm diameter colloidal particles via a low-temperature (∼80 °C) hydrothermal process using a flow reactor. The effects of the pH of the reaction solution as well as the additive used on the 3D epitaxy process are investigated. The optical and electrical properties of the epitaxially grown nanostructured ZnO are probed by reflectance, photoluminescence, and Hall effect measurements. It is found that the epitaxially grown nanostructured ZnO generally exhibits properties superior to those of polycrystalline ZnO. The demonstrated hydrothermal epitaxy process should be applicable to other chemical solution-based deposition techniques and help extend the range of materials that can be grown into a 3D nanostructured single-crystalline form

Reduced Graphene Oxide/LiI Composite Lithium Ion Battery Cathodes

Li-iodine chemistry is of interest for electrochemical energy storage because it has been shown to provide both high power and high energy density. However, Li-iodine batteries are typically formed using Li metal and elemental iodine, which presents safety and fabrication challenges (e.g., the high vapor pressure of iodine). These disadvantages could be circumvented by using LiI as a starting cathode. Here, we present fabrication of a reduced graphene oxide (rGO)/LiI composite cathode, enabling for the first time the use of LiI as the Li-ion battery cathode. LiI was coated on rGO by infiltration of an ethanolic solution of LiI into a compressed rGO aerogel followed by drying. The free-standing rGO/LiI electrodes show stable long-term cycling and good rate performance with high specific capacity (200 mAh g^–1 at 0.5 C after 100 cycles) and small hysteresis (0.056 V at 1 C). Shuttling was suppressed significantly. We speculate the improved electrochemical performance is due to strong interactions between the active materials and rGO, and the reduced ion and electron transport distances provided by the three-dimensional structured cathode

General Method for Forming Micrometer-Scale Lateral Chemical Gradients in Polymer Brushes

We report a general diffusion based method to form micrometer-scale lateral chemical gradients in polymer brushes via selective alkylation. A quaternized brush gradient is derived from a concentration gradient of alkylating agent formed by diffusion in permeable media around a microchannel carrying the alkylating agent. Polymer brushes containing both charge and aromatic gradients are formed using the alkylating agents, methyl iodide and benzyl bromide, respectively. The gradients are quantitatively characterized by confocal Raman spectroscopy and qualitatively by fluorescence microscopy. The length and gradient strength can be controlled by varying the diffusion time, concentrations, and solvents of the alkylating agent solutions. This microfluidic brush gradient generation method enables formation of 2-D chemical potential gradients with a diversity of shapes

Extremely Durable, Flexible Supercapacitors with Greatly Improved Performance at High Temperatures

The reliability and durability of energy storage devices are as important as their essential characteristics (<i>e.g.</i>, energy and power density) for stable power output and long lifespan and thus much more crucial under harsh conditions. However, energy storage under extreme conditions is still a big challenge because of unavoidable performance decays and the inevitable damage of components. Here, we report high-temperature operating, flexible supercapacitors (f-SCs) that can provide reliable power output and extreme durability under severe electrochemical, mechanical, and thermal conditions. The outstanding capacitive features (<i>e.g.</i>, ∼40% enhancement of the rate capability and a maximum capacitances of 170 F g^–1 and 18.7 mF cm^–2 at 160 °C) are attributed to facilitated ion transport at elevated temperatures. Under high-temperature operation and/or a flexibility test in both static and dynamic modes at elevated temperatures >100 °C, the f-SCs showed extreme long-term stability of 100000 cycles (>93% of initial capacitance value) and mechanical durability after hundreds of bending cycles (at bend angles of 60–180°). Even at 120 °C, the versatile design of tandem serial and parallel f-SCs was demonstrated to provide both desirable energy and power requirements at high temperatures

Extremely Durable, Flexible Supercapacitors with Greatly Improved Performance at High Temperatures

The reliability and durability of energy storage devices are as important as their essential characteristics (<i>e.g.</i>, energy and power density) for stable power output and long lifespan and thus much more crucial under harsh conditions. However, energy storage under extreme conditions is still a big challenge because of unavoidable performance decays and the inevitable damage of components. Here, we report high-temperature operating, flexible supercapacitors (f-SCs) that can provide reliable power output and extreme durability under severe electrochemical, mechanical, and thermal conditions. The outstanding capacitive features (<i>e.g.</i>, ∼40% enhancement of the rate capability and a maximum capacitances of 170 F g^–1 and 18.7 mF cm^–2 at 160 °C) are attributed to facilitated ion transport at elevated temperatures. Under high-temperature operation and/or a flexibility test in both static and dynamic modes at elevated temperatures >100 °C, the f-SCs showed extreme long-term stability of 100000 cycles (>93% of initial capacitance value) and mechanical durability after hundreds of bending cycles (at bend angles of 60–180°). Even at 120 °C, the versatile design of tandem serial and parallel f-SCs was demonstrated to provide both desirable energy and power requirements at high temperatures

Photoelectrochemical Behavior of Hierarchically Structured Si/WO₃ Core–Shell Tandem Photoanodes

WO₃ thin films have been deposited in a hierarchically structured core–shell morphology, with the cores consisting of an array of Si microwires and the shells consisting of a controlled morphology WO₃ layer. Porosity was introduced into the WO₃ outer shell by using a self-assembled microsphere colloidal crystal as a mask during the deposition of the WO₃ shell. Compared to conformal, unstructured WO₃ shells on Si microwires, the hierarchically structured core–shell photoanodes exhibited enhanced near-visible spectral response behavior, due to increased light absorption and reduced distances over which photogenerated carriers were collected. The use of structured substrates also improved the growth rate of microsphere-based colloidal crystals and suggests strategies for the use of colloidal materials in large-scale applications