Jingying Zhai

pH Independent Nano-Optode Sensors Based on Exhaustive Ion-Selective Nanospheres

Bulk optode-based ion selective optical sensors work on the basis of extraction equilibria, and their response toward the analyte ion is known to dependent on the sample pH. This pH dependence has been one of the major disadvantages that have hampered the broad acceptance of bulk optodes in chemical sensing. We present here for the first time the use of exhaustive Ca(2+)-selective nanosensors that may overcome this pH dependent response. The nanosensors were characterized at different pH and the same linear calibration was obtained in the Ca(2+) concentration range from 10(-7) M to 10(-5) M.

Potentiometric response from ion-selective nanospheres with voltage-sensitive dyes.

Potentiometric sensors require the implementation of conducting wires for signal transduction, but this is impractical for the readout of individual nanoparticles. It is here demonstrated for the first time that the potentiometric response of ion-selective nanospheres can be observed with voltage-sensitive dyes, thereby converting nanoscale electrochemical signals into an optical readout. No reference electrode is needed since the readout is by fluorescence. The results strongly support the potentiometric origin for the fluorescence response. The ion-selective nanospheres exhibit excellent selectivity and respond to ion concentration changes independent of sample pH, providing a new platform of potentiometric nanosensors with optical readout compatible with optical imaging equipment.

Ionophore-Based Ion-Selective Optical NanoSensors Operating in Exhaustive Sensing Mode

Ion selective optical sensors are typically interrogated under conditions where the sample concentration is not altered during measurement. We describe here an alternative exhaustive detection mode for ion selective optical sensors. This exhaustive sensor concept is demonstrated with ionophore-based nanooptodes either selective for calcium or the polycationic heparin antidote protamine. In agreement with a theoretical treatment presented here, linear calibration curves were obtained in the exhaustive detection mode instead of the sigmoidal curves for equilibrium-based sensors. The response range can be tuned by adjusting the nanosensor loading. The nanosensors showed average diameters of below 100 nm and the sensor response was found to be dramatically faster than that for film-based optodes. Due to the strong binding affinity of the exhaustive nanosensors, total calcium concentration in human blood plasma was successfully determined. Optical determination of protamine in human blood plasma using the exhaustive nanosensors was attempted, but was found to be less successful.

Ion-Selective Optode Nanospheres as Heterogeneous Indicator Reagents in Complexometric Titrations

Traditionally, optical titrations of inorganic ions are based on a rapid and visible color change at the end point with water-soluble organic dyes as indicators. Adequate selectivity is required for both the indicator and the complexing agent, which is often limited. We present here alternative, heterogeneous ionophore-based ion-selective nanospheres as indicators and chelators for optical titrations. The indicating nanospheres rely on a weaker extraction of the analyte of interest by ion-exchange, owing to the additional incorporation of a lipophilic pH indicator in the nanosphere core. Ca(2+) titration was demonstrated as a proof-of-concept. Both the chelating and the indicating nanospheres showed good selectivity and a wide working pH range.

Ion-Selective Optical Nanosensors Based on Solvatochromic Dyes of Different Lipophilicity: From Bulk Partitioning to Interfacial Accumulation

The sensing mechanism of fluorescent ion-selective nanosensors incorporating solvatochromic dyes (SDs), with K+ as model ion, is shown to change as a function of dye lipophilicity. Water-soluble SDs obey bulk partitioning principles where the sensor response directly depends on the lipophilicity of the SD and exhibits an influence on the phase volume ratio of nanosensors to aqueous solution (dilution effect). A lipophilization of the SDs is shown to overcome these limitations. An interfacial accumulation mechanism is proposed and confirmed with Förster resonance energy transfer (FRET) with a ratiometric near-infrared fluorescence FRET pair. This work lays the foundation for operationally more robust ion-selective nanosensors incorporating SDs.

Anion-exchange nanospheres as titration reagents for anionic analytes.

We present here anion-exchange nanospheres as novel titration reagents for anions. The nanospheres contain a lipophilic cation for which the counterion is initially Cl(-). Ion exchange takes place between Cl(-) in the nanospheres and a more lipophilic anion in the sample, such as ClO4(-) and NO3(-). Consecutive titration in the same sample solution for ClO4(-) and NO3(-) were demonstrated. As an application, the concentration of NO3(-) in spinach was successfully determined using this method.

Determination of pKa Values of Hydrophobic Colorimetric pH Sensitive Probes in Nanospheres

A simple and novel method is proposed here for the first time to determine pK(a) values of chromogenic hydrophobic pH sensitive probes directly in nanospheres. pK(a) values can be obtained by measuring the pH response of the nanospheres (containing the probes and ion exchanger) followed by measuring the pH and Na(+) responses of the nanospheres (containing solvatochromic dyes and ion exchanger). The pK(a) values of four chromoionophores were successfully determined. This method is in principle also applicable to characterize colorimetric probes in other water immiscible nanomaterials.

Ionophore-based titrimetric detection of alkali metal ions in serum

While the titrimetric assay is one of the most precise analytical techniques available, only a limited list of complexometric chelators is available, as many otherwise promising reagents are not water-soluble. Recent work demonstrated successful titrimetry with ion-exchanging polymeric nanospheres containing hydrophobic complexing agents, so-called ionophores, opening an exciting avenue in this field. However, this method was limited to ionophores of very high affinity to the analyte and exhibited a relatively limited titration capacity. To overcome these two limitations, we report here on solvent based titration reagents. This heterogeneous titration principle is based on the dissolution of all hydrophobic recognition components in a solvent such as dichloromethane (CH2Cl2) where the ionophores are shown to maintain a high affinity to the target ions. HSV (hue, saturation, value) analysis of the images captured with a digital camera provides a convenient and inexpensive way to determine the end point. This approach is combined with an automated titration setup. The titrations of the alkali metals K+, Na+, and Li+ in aqueous solution are successfully demonstrated. The potassium concentration in human serum without pretreatment was precisely and accurately determined as 4.38 mM ± 0.10 mM (automated titration), which compares favorably with atomic emission spectroscopy (4.47 mM ± 0.20 mM).

Solvatochromic Dyes as pH-Independent Indicators for Ionophore Nanosphere-Based Complexometric Titrations.

For half a century, complexometric titrations of metal ions have been performed with water-soluble chelators and indicators that typically require careful pH control. Very recently, ion-selective nanosphere emulsions were introduced that exhibit ion-exchange properties and are doped with lipophilic ionophores originally developed for chemical ion sensors. They may serve as novel, highly selective and pH independent complexometric reagents. While ion optode emulsions have been demonstrated as useful indicators for such titrations, they exhibit a pH cross-response that unfortunately complicates the identification of the end point. Here, we present pH-independent optode nanospheres as indicators for complexometric titrations, with calcium as an initial example. The nanospheres incorporate an ionic solvatochromic dye (SD), ion exchanger and ionophore. The solvatochromic dye will be only expelled from the core of the nanosphere into the aqueous solution at the end point at which point it results in an optical signal change. The titration curves are demonstrated to be pH-independent and with sharper end points than with previously reported chromoionophore-based optical nanospheres as indicator. The calcium concentration in mineral water was successfully determined using this method.

Reversible pH-independent optical potassium sensor with lipophilic solvatochromic dye transducer on surface modified microporous nylon

A reversible and pH-independent fluorescent ion optode is introduced with an ionophore and surface confined solvatochromic dye transducer doped onto microporous nylon membranes. The resulting film responds to K+ with excellent selectivity over the range of 10-7 to 10-2 M and a response time of t95 < 60 s above 10-6 M.