Xiaojiang Xie

Reversible Photodynamic Chloride-Selective Sensor Based on Photochromic Spiropyran

We report here for the first time on a reversible photodynamic bulk optode sensor based on the photoswitching of a spiropyran derivative (Sp). The photoswitching of Sp induces a large basicity increase in the polymeric phase, which triggers the extraction of Cl– and H+. Cl– is stabilized by a lipophilic chloride-selective ionophore inside the membrane, while H+ binds with the open form of Sp and induces a spectral change, hence providing the sensor signal. The system was studied with spectroscopic and electrochemical methods.

Direct Optical Carbon Dioxide Sensing Based on a Polymeric Film Doped with a Selective Molecular Tweezer-Type Ionophore

A novel optical method for the determination of CO(2) concentration in aqueous and gaseous samples of plasticized PVC film is presented. The detection principle makes use of a direct molecular recognition of the carbonate ion by a molecular tweezer-type ionophore, which has previously been demonstrated to exhibit excellent carbonate selectivity. The carbonate ion is extracted together with hydrogen ions into a polymeric film that contains the anion exchanger tridodecylmethylammonium chloride, a lipophilic, electrically charged, and highly basic pH indicator, which is used for the readout in absorbance mode, in addition to the lipophilic carbonate ionophore. According to known bulk optode principles, such an optical sensor responds to the product of the carbonate ion activity and the square of hydrogen ion activity. This quantity is thermodynamically linked to the activity of carbon dioxide. This allows one to realize a direct carbon dioxide sensor that does not make use of the traditional Severinghaus sensing principle of measuring a pH change upon CO(2) equilibration across a membrane. A selectivity analysis shows that common ions such as chloride are sufficiently suppressed for direct PCO(2) measurements in freshwater samples at pH 8. Chloride interference, however, is too severe for direct seawater measurements at the same pH. This may be overcome by placing a gas-permeable membrane over the optode sensing film. This is conceptually confirmed by establishing that the sensor is equally useful for gas-phase PCO(2) measurements. As expected, humid air samples are required for proper sensor functioning, as dry CO(2) gas will not cause any signal change. The sensor showed acceptable response times and good reproducibility under both conditions.

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.

Ultrasmall fluorescent ion-exchanging nanospheres containing selective ionophores.

We present a convenient precipitation procedure to fabricate ultrasmall fluorescent ion-selective nanosensors that operate on the basis of bulk ion-exchange sensing principles. The nanosphere matrix is composed of bis(2-ethylhexyl) sebacate (DOS) and a triblock copolymer Pluronic(®) F-127, which also functions as a surfactant to stabilize the nanoparticle. The particles can be prepared easily in large quantity without resorting to further complicated purification. Dynamic light scattering shows that these particles have a monodisperse size distribution with an average diameter of ∼40 nm, suggesting that the nanoparticles are among the smallest ionophore-based ion-selective nanosensors reported to date. A newly reported oxazinoindoline (Ox) as well as a Nile blue derivative (chromoionophore I) was used as a chromoionophore. Na(+)- and H(+)-selective nanospheres were characterized by absorbance and fluorescence spectroscopy. Owing to the very small size of the nanospheres, the suspension containing the particles is transparent. In the additional presence of the pH indicator HPTS, spectroscopic interrogation of pH and Na(+) in the same sample was demonstrated. As an example, the nanospheres were used to measure the Na(+) level in commercial mineral waters, and the results showed good agreement with atomic absorption spectroscopy (AAS).

Non-Severinghaus Potentiometric Dissolved CO2 Sensor with Improved Characteristics

A new type of carbon dioxide sensor comprising a pH glass electrode measured against a carbonate-selective membrane electrode based on a tweezer type carbonate ionophore is presented here for the first time. No cumbersome liquid junction based reference element is utilized in this measurement. The sensor shows an expected nernstian divalent response slope to dissolved CO(2) over a wide range covering the routine environmental and physiological PCO(2) levels. Unlike the conventional Severinghaus CO(2) probe for which the response is substantially delayed to up to 10 min due to diffusion of carbon dioxide into the internal compartment, the ion-selective CO(2) sensor proposed here shows a response time (t(95%)) of 5 s. When used together with a traditional reference electrode, the sensor system is confirmed to also monitor sample pH and carbonate along with carbon dioxide. A selectivity analysis suggests that Cl(-) does not interfere even at high concentrations, allowing one to explore this type of sensor probe for use in seawater or undiluted blood samples. The CO(2) probe has been used in an aquarium to monitor the CO(2) levels caused by the diurnal cycles caused by the metabolism of the aquatic plants and shows stable and reproducible results.

Photoresponsive Ion Extraction/Release Systems: Dynamic Ion Optodes for Calcium and Sodium Based on Photochromic Spiropyran

Photoresponsive ion extraction/release systems (PRIONERS) represent a highly interesting tool for the localized and time-controlled chemical perturbation of biological materials. We report here on our first results on phototriggered calcium and sodium exchanging materials. Such materials exist in two distinct states (“on” and “off”), depending on the wavelength of illumination. We used a combination of spectroscopic and electrochemical methods to obtain a better understanding of the dynamic processes involved in the triggered ion-exchange reaction upon activation of the photoactive compound. The driving force for the ion exchange is the light-induced acidity change of the chromoionophore. Activation with UV light generates a species in the membrane with an increased pKa. Protons are pulled into the membrane, and at the same time, ions are expelled. The selectivity of the system is determined by the employed ionophore. In contrast to photoresponsive ionophore-based systems, the concept presented here is applicable for virtually any ion of interest for which an ionophore exists.

Ion selective optodes: from the bulk to the nanoscale

AbstractThis review describes recent advances in the miniaturization of ion selective optodes into microscale and nanoscale sensors. The topics include a comparison between film-based and miniaturized ion optodes, equilibrium and exhaustive detection modes, recent preparation methodologies and applications of microscale and nanoscale ion optodes, criteria for the design of optode sensors, and other future perspectives. Graphical AbstractIon selective optodes are attractivre optical sensing tools for ionic species. This review highlights recent advances with this class of ion selective optical sensors with a focus on miniaturization, characteristics and applications of micrometer and nanometer sized optode sensors

Light-Controlled Reversible Release and Uptake of Potassium Ions from Ion-Exchanging Nanospheres

Here, we report for the first time on photoswitchable nanospheres containing spiropyran (Sp) for reversible release and uptake of metal ions. K(+) is used as a model ion to demonstrate the chemical principle of this approach. Valinomycin is incorporated in the nanospheres to stabilize K(+). Upon UV illumination, Sp transforms to the more basic ring-opened merocyanine form, which takes up H(+) from the surrounding aqueous solution and expels K(+) from the nanospheres. The process can be reversed by irradiation with visible light to reduce the surrounding K(+) concentration.

Photoelectric Conversion Based on Proton-Coupled Electron Transfer Reactions

Making efficient use of solar energy is one of the biggest challenges of our time. In nature, solar energy can be harvested by photosynthesis where proton-coupled electron transfer (PCET) plays a critical role. Here, PCET is utilized for the first time to directly convert light energy to electrical energy. Quinone/hydroquinone PCET redox couples were used to produce a photovoltage along with spiropyrans, photoswitchable compounds that undergo reversible transformation between a ring-closed (Sp) and ring-opened form (Mc). The Mc form is more basic than the Sp form, and the open-circuit voltage (V(oc)) is related to the proton concentration and that of the Sp/Mc ratio controlled by light. V(oc) values from 100 to 140 mV were produced. In addition to direct current (J(sc) ca. 9 μA cm(-2)), alternating current in the range of 0.1 to 200 Hz was also produced by manipulating the input light.

Chronopotentiometric Carbonate Detection with All-Solid-State Ionophore-Based Electrodes

We present here for the first time an all-solid-state chronopotentiometric ion sensing system based on selective ionophores, specifically for the carbonate anion. A chronopotentiometric readout is attractive because it may allow one to obtain complementary information on the sample speciation compared to zero-current potentiometry and detect the sum of labile carbonate species instead of only ion activity. Ferrocene covalently attached to the PVC polymeric chain acts as an ion-to-electron transducer and provides the driving force to initiate the sensing process at the membrane-sample interface. The incorporation of a selective ionophore for carbonate allows one to determine this anion in a background electrolyte. Various inner electrolyte and all-solid-state-membrane configurations are explored, and localized carbonate depletion is only observed for systems that do not contain ion-exchanger additives. The square root of the transition times extracted from the inflection point of the chronopotentiograms as a function of carbonate specie concentration follows a linear relationship. The observed linear range is 0.03-0.35 mM in a pH range of 9.50-10.05. By applying the Sand equation, the diffusion coefficient of carbonate is calculated as (9.03 ± 0.91) 10(-6) cm(2) s(-1), which corresponds to the established value. The reproducibility of assessed carbonate is better than 1%. Additionally, carbonate is monitored during titrimetric analysis as a precursor to an in situ environmental determination. Based on these results, Fc-PVC membranes doped with ionophores may form the basis of a new family of passive/active all-solid-state ion selective electrodes interrogated by a current pulse.