Broad Range pH Sensor Research Articles

A fluorescent PET probe based on polyethyleneimine-Ag nanoclusters as a reversible, stable and selective broad-range pH sensor

In this work, nanoclusters (NCs) of Cu and Ag capped with hyperbranched polyethyleneimine (PEI) were prepared using chemical reduction by a one-step hydrothermal method. The PEI coated-NCs were characterized by high-resolution transmission electron microscopy, ζ potential, thermogravimetric analysis, dynamic light scattering, Fourier-transform infrared, UV-visible, and fluorescence spectroscopy. The PEI-NCs exhibited strong absorption and fluorescence, high stability, and excellent water dispersibility. The resulting PEI-NCs showed a reversible and linear response of fluorescence intensity with pH over a wide range (3-11); however, PEI-AgNCs showed a better reversibility and sensitivity than PEI-CuNCs. Unlike several types of pH sensors based on modified NCs, which are based on a nanoparticle aggregation/disaggregation mechanism, the response of our sensor is based on a photoinduced electron transfer process, which gives it a high reversibility. This method was successfully applied in pH measurements in tap water and green tea samples, with excellent results, indicating its practical utility for these applications. A visual device was obtained by immobilizing PEI-AgNCs into agarose hydrogels at different pH values. The results show that the proposed sensor can be used as a pH visual detector. Besides, the light emission of the nanosensor was corroborated by fluorescence microscopy, confirming that the nanosensor based on PEI-AgNCs has great potential to be used in cellular imaging.

Tuning the p Ka of a pH Responsive Fluorophore and the Consequences for Calibration of Optical Sensors Based on a Single Fluorophore but Multiple Receptors.

Since Sørensen and Bjerrum defined the pH scale, we have relied on two methods for determining pH, the colorimetric or the electrochemical. For pH electrodes, calibration is easy as a linear response is observed in the interesting pH range from 1 to ∼12. For colorimetric sensors, the response follows the sigmoidal Bjerrum diagram of an acid-base equilibrium. Thus, calibration of colorimetric sensors is more complex. Here, seven pH responsive fluorescent dyes based on the same diazaoxatriangulenium (DAOTA) fluorophore linked to varying receptor groups were prepared. Photoinduced electron transfer (PeT) quenching from appended aniline or phenol receptors generated the pH response of the DAOTA dyes, and the position of the p Ka value of the dye was tuned using the Hammett relationship as a guideline. The fluorescence intensity of the dyes in a sol-gel matrix environment was measured as a function of pH in universal buffer, and it was found that the dyes behave as perfect pH responsive probes under these conditions. The response of optical pH sensors is nonlinear and was found to be limited to 2-3 pH units for a precision of 0.01 pH unit. As sensors with a broader sensitivity range can be achieved by mixing multiple dyes with different p Ka values, mixtures of dyes in solution were investigated, and a broad range pH sensor with a precision of 0.006 pH units over a range of 3.6 pH units was demonstrated. Further, approximating the sensor response as linear was considered, and a limiting precision for this approach was determined. As the responses of the pH responsive DAOTA dyes were found to be ideally sigmoidal and as the six dyes were shown to have p Ka values scattered over a range from ∼2 to ∼9, this allows for design of a broad range optical pH sensor in the pH range from 1 to 10. This hypothesis was tested using quaternary mixtures of the different DAOTA dyes, and these were found to behave as a direct sum of the individual components. Thus, while linear calibration is limited to a precision of 0.02 in a range of 2-3 pH units, calibration using ideal sigmoidal functions is possible in the range of 1-10 with a precision better than 0.01, and as good as 0.002 pH units.

Synthesis of luminescent Cu9S5 nanoclusters from copper-2,5-dimercapto-1,3,4-thiadiazole coordination polymer as pH sensor

Abstract Cu9S5 nanoclusters (Cu9S5 NCs) with photoluminescence emission in the visible region have been synthesized via a simple treatment of copper-2, 5-dimercapto-1, 3, 4-thiadiazole (Cu(II)-DMTD) coordination polymer with ammonium hydroxide. This procedure involves a desulfurative C-N cross-coupling route, in which one mercapto group was replaced by amine, resulting in 2-mercapto-5-amine-1,3,4-thiadiazole (AMTD) as protecting agent for Cu9S5 NCs. The product exhibits a fluorescence emission at 567 nm with a quantum yield (Φ) 0.068. The as-prepared Cu9S5 NCs were employed as a broad-range pH sensor by virtue of the fluorescence intensity responding sensitively to pH fluctuating in a linear range of 3.0–10.0.

Dual-Emitting Fluorescent Metal–Organic Framework Nanocomposites as a Broad-Range pH Sensor for Fluorescence Imaging

pH plays an important role in understanding physiological/pathologic processes, and abnormal pH is a symbol of many common diseases such as cancer, stroke, and Alzheimer's disease. In this work, an effective dual-emission fluorescent metal-organic framework nanocomposite probe (denoted as RB-PCN) has been constructed for sensitive and broad-range detection of pH. RB-PCN was prepared by encapsulating the DBI-PEG-NH2-functionalized Fe3O4 into Zr-MOFs and then further reacting it with rhodamine B isothiocyanates (RBITC). In RB-PCN, RBITC is capable of sensing changes in pH in acidic solutions. Zr-MOFs not only enrich the target analyte but also exhibit a fluorescence response to pH changes in alkaline solutions. Based on the above structural and compositional features, RB-PCN could detect a wide range of pH changes. Importantly, such a nanoprobe could "see" the intracellular pH changes by fluorescence confocal imaging as well as "measure" the wider range of pH in actual samples by fluorescence spectroscopy. To the best of our knowledge, this is the first time a MOF-based dual-emitting fluorescent nanoprobe has been used for a wide range of pH detection.

Fluorescence Ratiometric Optical Broad Range pH Sensor Based on CdSe/ZnS Quantum Dots and O170 Embedded in Ethyl Cellulose Matrix

This paper presents a ratiometric optical broad range pH sensor that comprises an optical fiber coated at one end with CdSe/ZnS quantum dots (QDs) and Oxazine 170 perchlorate (O170) embedded in ethyl cellulose (EC) matrix. The feasibility of coating an optical fiber with the sensing film to fabricate a ratiometric fiber optic broad range pH sensor is investigated. Using an LED with a central wavelength 405 nm as an excitation light source, the CdSe/ZnS QDs shows that the fluorescence intensity at 575 nm decreases with increasing pH and O170 shows the fluorescence intensity at 655 nm increases with increasing pH. The ratio of fluorescence intensities at 575 and 655 nm has a linear relationship with pH value in the 1.6–13.2 range. The ratiometric sensing approach presented in this study has the advantage of suppressing spurious fluctuations in the intensity of the excitation source and optical transmission properties of the optical fiber.

Glutathione-stabilized Cu nanoclusters as fluorescent probes for sensing pH and vitamin B1

Glutathione (GSH), playing roles as both a reducing reagent and protecting ligand, has been successfully employed for synthesizing Cu nanoclusters (CuNCs@GSH) on the basis of a simple and facile approach. The as-prepared CuNCs exhibited a fluorescence emission at 600nm with a quantum yield (QY) of approximately 3.6%. Subsequently, the CuNCs described here was employed as a broad-range pH sensor by virtue of the fluorescence intensity of CuNCs responding sensitively to pH fluctuating in a linear range of 4.0–12.0. Meanwhile, these prepared CuNCs were applied for detections of vitamin B1 (VB1) on the basis of positively charged VB1 neutralizing the negative surface charge of CuNCs, thus leading to the instability and aggregations of CuNCs, and further facilitating to quench their fluorescence. In addition, the proposed analytical method permitted detecting VB1 with a linear range of 2.0×10−8–1.0×10−4molL−1 as well as a detection limit of 4.6×10−9molL−1. Eventually, the practicability of this sensing approach was validated by assaying VB1 in human urine samples and pharmaceutical tablets, confirming its potential to broaden avenues for assaying VB1.

A broad range fluorescent pH sensor based on hollow mesoporous silica nanoparticles, utilising the surface curvature effect.

In this study, a broad range pH sensor was synthesized by loading the pH sensitive dye, fluorescein isothiocyanate (FITC), and a reference dye, rhodamine B isothiocyanate (RITC), into the mesostructure of hollow mesoporous silica nanoparticles (HMSNs) synthesized using a co-condensation method. Compared to a pH sensor based on the same pair of dyes on conventional mesoporous silica nanoparticles (MSNs), this dual-labeled pH sensor based on HMSNs shows a larger pH sensitive range, between 4.5 and 8.5, because of its broad surface curvature distribution which has a strong effect on the apparent pKa values of the FITC dye. The hollow mesoporous silica-dye nanoparticles were used to monitor intracellular pH via a ratiometric fluorescence method. The confocal images demonstrated the capacity of this broad range sensor which can differentiate simultaneously the local pH between various environments, for example, in the medium (pH = 7.2), cytosol (pH ∼ 7) and the endosome-lysosome pathway (pH = 4-5.5).

Broad range pH sensor based on sol–gel entrapped indicators on fibre optic

A broad-range fibre optic pH sensor based on evanescent wave absorption is presented in this paper. This sensor is prepared by immobilizing a mixture of three pH sensitive indicators (dyes): cresol red, bromophenol blue and chlorophenol red onto the unclad fibre surface using a sol–gel cladding technology. Triton is introduced into the sol–gel cladding to improve the cladding quality. Smooth and strong sol–gel cladding with entrapped indicators and triton has been fabricated and observed using a scanning electron microscope (SEM), an energy dispersive X-ray detector (EDX) and an atomic force microscopy (AFM). The pH sensor based the cladding has shown a linear, reversible and repeatable response over a broad range of pH values between 4.5 and 13.0.

A fiber-optic broad-range pH sensor system for gastric measurements

Abstract The construction and performance of a fiber-optic broad-range pH sensor system are described. The general construction of the sensor is similar to the original fiber-optic pH sensor, but two dyes with three p K values have been immobilized to provide resonse over the pH range of 0.5–7 with a precision better than 0.1 pH unit. The range extends to pH9 with less precision. The primary objective of the design is for gastric measurements. The system is based on absorbance dyes bound to polyacrylamide gel containing light-scattering particles. The sensor is constructed on a single 0.25-mm diameter plastic optical fiber. The optical system consists of a tungsten lamp, fiber-optic splitter and CCD/grating detector connected to a computer for spectral analysis, using two wavelength regions. The computer displays the pH graphically over 24 h. The system shows stability within 0.2 pH unit over 24 h, and has been tested with gastric samples in a dog.

The possible danger of excessive early maternal vocal stimulation on infant development

The construction and performance of a fiber-optic broad-range pH sensor system are described. The general construction of the sensor is similar to the original fiber-optic pH sensor, but two dyes with three pK values have been immobilized to provide resonse over the pH range of 0.5–7 with a precision better than 0.1 pH unit. The range extends to pH9 with less precision. The primary objective of the design is for gastric measurements. The system is based on absorbance dyes bound to polyacrylamide gel containing light-scattering particles. The sensor is constructed on a single 0.25-mm diameter plastic optical fiber. The optical system consists of a tungsten lamp, fiber-optic splitter and CCD/grating detector connected to a computer for spectral analysis, using two wavelength regions. The computer displays the pH graphically over 24 h. The system shows stability within 0.2 pH unit over 24 h, and has been tested with gastric samples in a dog.