Imaging fiber microarray fluorescent ion sensors based on bulk optode microspheres

Abstract Optical imaging fibers with micrometer-sized wells were used as a sensing platform for the development of microarray optical ion sensors based on selective bulk extraction principles established earlier for optodes. Uniform 10 μm sized microspheres based on plasticized poly(vinyl chloride) containing various combinations of ionophores, fluoroionophores and lipophilic ion-exchangers were prepared for the detection of sodium, potassium, calcium and chloride, and deposited onto the wells of etched fiber bundles. Specifically, sodium sensing particles were based on tert -butylcalix[4]arene tetraacetic acid tetraethylester, potassium particles on 2-dodecyl-2-methyl-1,3-propanediyl bis[ N -[5′-nitro(benzo-15-crown-5)-4′-yl]carbamate] (BME-44), calcium particles on an acrylic derivative of ETH 129 (AU-1) covalently attached to a methacrylic polymer, and chloride particles based on the anticrown ionophore [9]mercuracarborand-3 (MC-3). The fluorescence emission characteristics of individual microspheres were observed from the backside of the fibers and were found to selectively and rapidly change as a function of the sample composition. The optical characteristics of the particles were found to be comparable to that of corresponding thin optode films and particles deposited onto microscope glass slides. The measuring ranges (logarithmic molar concentrations) at pH 7.0 were found as −3 to 0 for sodium, −3.5 to −0.5 for potassium, −7 to −2 for calcium, and −5 to 0.5 for chloride. Selectivities were determined over other common electrolytes and found to be sufficient for physiological applications. The simultaneous deposition of sodium and chloride sensing particles was successfully performed, demonstrating that such microarray sensors are capable of simultaneously sensing multiple analytes. This technology is compatible with other microsphere-based fluorescent sensing principles, forming a promising total analysis platform for a variety of applications.

[1]  Eric Bakker,et al.  Mechanistic insights into the development of optical chloride sensors based on the [9]mercuracarborand-3 ionophore. , 2003, Analytical chemistry.

[2]  E. Bakker,et al.  A copolymerized dodecacarborane anion as covalently attached cation exchanger in ion-selective sensors. , 2003, Analytical chemistry.

[3]  R. Kopelman,et al.  Nitrite- and chloride-selective fluorescent nano-optodes and in vitro application to rat conceptuses. , 1998, Analytical chemistry.

[4]  I. Tsagkatakis,et al.  Flow cytometric ion detection with plasticized poly(vinyl chloride) microspheres containing selective lonophores. , 2002, Analytical chemistry.

[5]  D. Walt,et al.  High-density, microsphere-based fiber optic DNA microarrays. , 2003, Biosensors & bioelectronics.

[6]  Yu Qin,et al.  Plasticizer-free microspheres for ionophore-based sensing and extraction based on a methyl methacrylate-decyl methacrylate copolymer matrix , 2003 .

[7]  D R Walt,et al.  Combined imaging and chemical sensing using a single optical imaging fiber. , 1995, Analytical chemistry.

[8]  D R Walt,et al.  Dual-analyte fiber-optic sensor for the simultaneous and continuous measurement of glucose and oxygen. , 1995, Analytical chemistry.

[9]  I. Tsagkatakis,et al.  Spatial and spectral imaging of single micrometer-sized solvent cast fluorescent plasticized poly(vinyl chloride) sensing particles. , 2001, Analytical chemistry.

[10]  B. Löchel,et al.  Electrodeposited Magnetic Alloys for Surface Micromachining , 1996 .

[11]  Kurt Seiler,et al.  Design of a novel calcium-selective optode membrane based on neutral ionophores , 1990 .

[12]  David R. Walt,et al.  Simultaneous monitoring of pH, CO2 and O2 using an optical imaging fiber , 1997 .

[13]  D. Walt,et al.  Combined imaging and chemical sensing of fertilization-induced acid release from single sea urchin eggs. , 1999, Analytical biochemistry.

[14]  M. Hawthorne,et al.  A Hexamethyl Derivative of [9]Mercuracarborand-3: Synthesis, Characterization, and Host−Guest Chemistry , 1996 .

[15]  Sabine Szunerits,et al.  Aluminum surface corrosion and the mechanism of inhibitors using pH and metal ion selective imaging fiber bundles. , 2002, Analytical chemistry.

[16]  E. Bakker,et al.  Optical chloride sensor based on [9]mercuracarborand-3 with massively expanded measuring range. , 2004, Talanta.

[17]  A. Radu,et al.  Plasticizer-free polymer containing a covalently immobilized Ca2+-selective ionophore for potentiometric and optical sensors. , 2003, Analytical chemistry.

[18]  David R. Walt,et al.  Ordered nanowell arrays , 1996 .

[19]  E. Bakker,et al.  Plasticizer‐Free Polymer Membrane Ion‐Selective Electrodes Containing a Methacrylic Copolymer Matrix , 2002 .

[20]  E. Bakker.  Selectivity comparison of neutral carrier-based ion-selective optical and potentiometric sensing schemes , 1997 .

[21]  D. S. Gill,et al.  Optical multibead arrays for simple and complex odor discrimination. , 2001, Analytical chemistry.

[22]  D R Walt,et al.  In situ fluorescence imaging of localized corrosion with a pH-sensitive imaging fiber. , 1997, Analytical chemistry.

[23]  E. Bakker,et al.  Mass-produced lonophore-based fluorescent microspheres for trace level determination of lead ions. , 2002, Analytical chemistry.

[24]  David R Walt,et al.  Optical imaging fiber-based single live cell arrays: a high-density cell assay platform. , 2002, Analytical chemistry.

[25]  E. Bakker,et al.  Selectivity of ion-sensitive bulk optodes , 1992 .

[26]  D R Walt,et al.  Application of high-density optical microwell arrays in a live-cell biosensing system. , 2000, Analytical biochemistry.

[27]  M. Shortreed,et al.  Fluorescent fiber-optic calcium sensor for physiological measurements. , 1996, Analytical chemistry.

[28]  I. Tsagkatakis,et al.  Cross-linked dodecyl acrylate microspheres: novel matrices for plasticizer-free optical ion sensing , 2001 .

[29]  L G Bachas,et al.  Mercuracarborand "anti-crown ether"-based chloride-sensitive liquid/polymeric membrane electrodes. , 1999, Analytical chemistry.

[30]  E. Bakker,et al.  Monodisperse plasticized poly(vinyl chloride) fluorescent microspheres for selective ionophore-based sensing and extraction. , 2001, Analytical chemistry.

[31]  Ernö Pretsch,et al.  Carrier-Based Ion-Selective Electrodes and Bulk Optodes. 1. General Characteristics. , 1997, Chemical reviews.

[32]  J. Tenovuo,et al.  Human Saliva: Clinical Chemistry and Microbiology , 2021 .

[33]  Helmut Föll,et al.  Processing of Three‐Dimensional Microstructures Using Macroporous n‐Type Silicon , 1996 .

[34]  D R Walt,et al.  High-density fiber-optic DNA random microsphere array. , 2000, Analytical chemistry.

[35]  D R Walt,et al.  Randomly ordered addressable high-density optical sensor arrays. , 1998, Analytical chemistry.

[36]  Tuan Vo-Dinh,et al.  Detection of cytochrome C in a single cell using an optical nanobiosensor. , 2004, Analytical chemistry.

[37]  J. Kauer,et al.  Convergent, self-encoded bead sensor arrays in the design of an artificial nose. , 1999, Analytical chemistry.

[38]  W. Simon,et al.  Design of anion-selective membranes for clinically relevant sensors , 1986 .

[39]  M. Shortreed,et al.  Miniature sodium-selective ion-exchange optode with fluorescent pH chromoionophores and tunable dynamic range. , 1996, Analytical chemistry.

[40]  David R Walt,et al.  High-density fiber-optic genosensor microsphere array capable of zeptomole detection limits. , 2002, Analytical chemistry.

[41]  D R Walt,et al.  Improved fiber-optic chemical sensor for penicillin. , 1995, Analytical chemistry.