We demonstrate a colorimetric glucose recognition material consisting of a crystalline colloidal array embedded within a polyacrylamide-poly(ethylene glycol) (PEG) hydrogel, or a polyacrylamide-15-crown-5 hydrogel, with pendent phenylboronic acid groups. We utilize a new molecular recognition motif, in which boronic acid and PEG (or crown ether) functional groups are prepositioned in a photonic crystal hydrogel, such that glucose self-assembles these functional groups into a supramolecular complex. The formation of the complex results in an increase in the hydrogel cross-linking, which for physiologically relevant glucose concentration blue shifts the photonic crystal diffraction. The visually evident diffraction color shifts across the visible spectral region over physiologically important glucose concentration ranges. These materials respond to glucose at physiological ionic strengths and pH values and are selective in their mode of response for glucose over galactose, mannose, and fructose. Thus, we have developed a new recognition motif for glucose that shows promise for the fabrication of noninvasive or minimally invasive in vivo glucose sensing for patients with diabetes mellitus.
We developed a carbohydrate sensing material, which consists of a crystalline colloidal array (CCA) incorporated into a polyacrylamide hydrogel (PCCA) with pendent boronic acid groups. The embedded CCA diffracts visible light, and the PCCA diffraction wavelength reports on the hydrogel volume. This boronic acid PCCA responds to species containing vicinal cis diols such as carbohydrates. This PCCA photonic crystal sensing material responds to glucose in low ionic strength aqueous solutions by swelling and red shifting its diffraction as the glucose concentration increases. The hydrogel swelling results from a Donnan potential due to formation of boronate anion; the boronic acid pK(a) decreases upon glucose binding. This sensing material responds to glucose and other sugars at <50 microM concentrations in low ionic strength solutions.
We developed a new sensing motif for the detection and quantification of creatinine, which is an important small molecule marker of renal dysfunction. This novel sensor motif is based on our intelligent polymerized crystalline colloidal array (IPCCA) materials, in which a three-dimensional crystalline colloidal array (CCA) of monodisperse, highly charged polystyrene latex particles are polymerized within lightly cross-linked polyacrylamide hydrogels. These composite hydrogels are photonic crystals in which the embedded CCA diffracts visible light and appears intensely colored. Volume phase transitions of the hydrogel cause changes in the CCA lattice spacings which change the diffracted wavelength of light. We functionalized the hydrogel with two coupled recognition modules, a creatinine deiminase (CD) enzyme and a 2-nitrophenol (2NPh) titrating group. Creatinine within the gel is rapidly hydrolyzed by the CD enzyme in a reaction which releases OH(-). This elevates the steady-state pH within the hydrogel as compared to the exterior solution. In response, the 2NPh is deprotonated. The increased solubility of the phenolate species as compared to that of the neutral phenols causes a hydrogel swelling which red-shifts the IPCCA diffraction. This photonic crystal IPCCA senses physiologically relevant creatinine levels, with a detection limit of 6 microM, at physiological pH and salinity. This sensor also determines physiological levels of creatinine in human blood serum samples. This sensing technology platform is quite general. It may be used to fabricate photonic crystal sensors for any species for which there exists an enzyme which catalyzes it to release H(+) or OH(-).
We developed a polymerized crystalline colloidal array photonic material that senses metal cations in water at low concentrations (PCCACS). Metal cations such as Cu2+, Co2+, Ni2+, and Zn2+ bind to 8-hydroxyquinoline groups covalently attached to the PCCACS. At low metal concentrations (
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