A Novel Water-soluble Ratiometric Fluorescent Probe Based on FRET for Sensing Lysosomal pH

A new ratiometric fluorescent probe based on Förster resonance energy transfer (FRET) for sensing lysosomal pH has been developed. The probe (RMPM) was composed of imidazo[1,5-α]pyridine quaternary ammonium salt fluorophore as the FRET donor and the rhodamine moiety as the FRET acceptor. It’s the first time to report that imidazo[1,5-α]pyridine quaternary ammonium salt acts as the FRET donor. The ratio of fluorescence intensity of the probe at two wavelengths (I₄₂₄/I₅₈₁) changed significantly and responded linearly toward minor pH changes in the range of 5.4–6.6. It should be noted that it’s rare to report that a ratiometric pH probe could detect so weak acidic pH with pKa = 6.31. In addition, probe RMPM exhibited excellent water-solubility, fast-response, all-right selectivity and brilliant reversibility. Moreover, RMPM has been successfully applied to sensing lysosomal pH in HeLa cells and has low cytotoxicity.     

An AIE-Active probe for detection and bioimaging of pH values based on lactone hydrolysis reaction

Cellular pH homeostasis is essential for many physiological and pathological processes. pH monitoring is helpful for the diagnosis, treatment and prevention of disorders and diseases. Herein, we developed a ratiometric fluorescent pH probe (TCC) based on a coumarin derivative containing a highly active lactone ring. TCC exhibited a typical AIE effect and emitted blue fluorescence under weak acidic condition. When under weak basic condition, the active lactone moiety underwent a hydrolysis reaction to afford a water-soluble product, which gave red-shifted emission. The emission color change from blue through cyan and then to yellow within pH 6.5–9.0 which is approximate to the biological pH range. And the fluorescence color change along with pH value is reversible. Furthermore, TCC was successfully utilized in the detection of the intracellular pH change of live HeLa cells, which indicated that TCC had practical potential in biomedical research.

     

Conformational flexibility of xanthene‐based covalently linked dimers

The conformational flexibility of three covalently linked dimers consisting of two xanthene‐based moieties connected by a diphenyl ether linker was studied using NMR spectroscopy, X‐ray crystallography, and density functional theory (DFT) calculations. The three dimers interconvert as a function of pH: the doubly cationic dimer (Xan⁺)₂ exists in acidic solutions (pH < 0.5), the mono‐alcohol monocation Xan⁺–Xan‐OH at intermediate pH values (pH = 1–3), and the neutral diol at the highest pH‐values (pH > 3). Each dimer exhibits conformational degrees of freedom associated with rotations of either the xanthene moiety or of the diphenyl ether (DPE) linker. The barriers for rotation of the xanthylium moiety were evaluated using DFT calculations, yielding values of 23 kcal/mol for (Xan⁺)₂ and 11 kcal/mol for (Xan‐OH)₂, respectively. The rotational barrier for the diphenyl ether linker in Xan⁺–Xan‐OH (15 kcal/mol) was experimentally determined using variable temperature NMR measurements. The relative orientation of the two –OH groups in (Xan‐OH)₂ diol was investigated in solution and the solid state using NMR spectroscopy and X‐ray crystallography. The conformer observed in the solid state was found to be the In–Out conformer, while free rotation of the xanthenol units is thought to occur on the NMR timescale at room temperature. These studies are relevant for the design of linkers for efficient water oxidation catalysts. Copyright © 2016 John Wiley & Sons, Ltd.     

Influence of pH in La-doped SnO2 nanoparticles towards sensor applications

The present investigation has been carried out to optimize the pH level of lanthanum (La)-doped tin dioxide (SnO₂) nanoparticles towards the potential application in gas sensor. The La-doped SnO₂ nanoparticles were synthesized by sol-gel method in different pH values varying from acidic to base nature. The synthesized nanoparticles were characterized by X-ray diffraction (XRD), ultraviolet (UV), photoluminescence (PL), and scanning electron microscopy (SEM) techniques. The XRD, UV, and PL analyses show the pH influences on the crystallite size of La-doped SnO₂ nanoparticles. The SEM images show the formation of porous structure at pH 11. Also, the electrical conductivity of 1 mol% La-doped SnO₂ at pH 3 and pH 11 were measured by impedance analyzer. In addition, we have fabricated and demonstrated device performance of synthesized La-doped SnO₂ nanoparticles for gas-sensing application. Real-time current response and long-time response to the gas sensing were also studied for the fabricated device.

     

Fiber-Optic pH Sensor

The new enhancement in the determination of pH using optical fiber system is described here. This work uses the membrane made of cellulose acetate membrane for reagent immobilization and congo red (pK _a 3.7) and neutral red (pK _a 7.2) as pH indicators. An effective covalent chemical binding procedure is used to immobilize the indicators. The response time, reversibility, linear range, reproducibility, and long-term stability of fiber optic sensor with congo red as well as neutral red have been determined. The linear range measured for the sensor based on the congo red and neutral red is 4.2–6.3 and 4.1–9.0, respectively. The response time of sensor membrane is measured by varying the substance pH values between 11.0 and 2.0.     

Scanning transmission X‐ray microscopy probe for in situ mechanism study of graphene‐oxide‐based resistive random access memory

Here, an in situ probe for scanning transmission X‐ray microscopy (STXM) has been developed and applied to the study of the bipolar resistive switching (BRS) mechanism in an Al/graphene oxide (GO)/Al resistive random access memory (RRAM) device. To perform in situ STXM studies at the C K‐ and O K‐edges, both the RRAM junctions and the I₀ junction were fabricated on a single Si₃N₄ membrane to obtain local XANES spectra at these absorption edges with more delicate I₀ normalization. Using this probe combined with the synchrotron‐based STXM technique, it was possible to observe unique chemical changes involved in the BRS process of the Al/GO/Al RRAM device. Reversible oxidation and reduction of GO induced by the externally applied bias voltages were observed at the O K‐edge XANES feature located at 538.2 eV, which strongly supported the oxygen ion drift model that was recently proposed from ex situ transmission electron microscope studies.     

FT-EPR study of the pH dependence of the photochemistry of sesamol in aqueous solution

A Fourier transform electron paramagnetic resonance (FT-EPR) study was made of the photochemistry of 3,4-methylenedioxyphenol (sesamol, SEOH)) in aqueous solution. FT-EPR measurements show that in alkaline (pH 11) solution, pulsed-laser excitation of SECT leads to photoionization giving the hydrated electron and SEO^⋅ free radical. Resonance signals from these paramagnetic species develop with instrument-controlled rise time. They exhibit a low-field emission/ high-field absorption (E/A) CIDEP pattern with the transition from emission to absorption occurring at the resonance of the hydrated electron. It is shown that the spin polarization stems from contributions from the ST₀ radical pair mechanism (E/A) and triplet mechanism (A). From this it is concluded that photoionization of sesamol occurs via the triplet excited state. In neutral and acidic (pH 4–7) aqueous solution, photoexcitation generates SEO^⋅ and cyclohexadienyl-type radicals. In this case, radicals grow in over a period of 1–2 μs and FT-EPR spectra display an E/A pattern with the inversion point in the center. The lowering of the pH of the solution apparently is accompanied by a strong reduction in the relative importance of photoionization. From the FT-EPR data it can be deduced that in neutral and acidic solutions the dominant reaction channel is H-atom transfer. In this respect, the photochemistry of sesamol differs from that of phenol andp-cresol. For these phenols the change in pH does not affect the appearance of the FT-EPR spectra. Apparently, the change in electronic structure caused by the methylenedioxy substituent strongly affects the excited state reactivity of sesamol.     

Incorporation of Siderophore Binding Sites in a Dipodal Fluorescent Sensor for Fe(III)

A new fluorescent probe 3, has been developed for the detection of Fe(III) in water based samples. The design of 3 involved the incorporation of Fe(III) binding sites observed in naturally occurring Siderophores into a synthetic sensing assembly. The probe, containing two Schiff base receptors connected to a mesitylene platform, was prepared in two steps. The dipodal sensor displayed good selectivity for Fe(III) when tested against other physiological and environmentally important metal ions, in HEPES buffered solution at pH 7.0, through a quenching of the fluorescent intensity. Stern-Volmer analysis of this quenching interaction indicated a 1:1 (host : guest) binding stoichiometry between the probe and Fe(III). The association constant, K _a calculated using the Benesi-Hildebrand equation was found to be 3.8 × 10⁴ M⁻¹. Crucially, the sensor was capable of measuring Fe(III) competitively in solutions containing both Fe(III) and Cu(II). Thus, the adoption of Fe(III) binding sites found in nature, into synthetic luminescent assemblies has proven an effective design strategy for the development of new Fe(III) probes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Dispersion of Nano TiO2 in Ethylene Glycol and Poly(ethylene terephthalate)

Nano TiO₂ was dispersed in ethylene glycol (EG) by the replacement of dispersion medium from water sol. EG/TiO₂ suspension was well stabilized by the electrostatic repulsive force when pH value of suspension was less than 4.3. In situ polymerization starting from bis(2-hydroxyethyl) terephthalate (BHET) and EG/TiO₂ suspension was carried out to prepare a series of poly(ethylene terephthalate) (PET)/TiO₂ nanocomposites. Under highly acidic conditions, 97% particles dispersed in PET matrix had the size less than 100 nm. With the increase of pH value, aggregation occurred and larger size particles appeared. A tensile test showed that Young's modulus of PET was increased by the addition of nano TiO₂     

Fluorescence study of the core/shell interface in polyelectrolyte micelles. Binding of fluorescent surfactants in the interfacial region

Properties of the interfacial region between the nonpolar core and the polar shell in polystyreneblock-poly (methacrylic acid) micelles were studied by fluorescence techniques using 5-(N-octadecanoyl) aminofluorescein (OAF) as a probe for microfluidity and local pH. The block copolymer used was tagged between blocks by one 9, 10-diphenylanthracene (DPA) group, which allowed us to study binding of OAF at the interface by means of nonradiative energy transfer between DPA and OAF. A shift in the pK _a of OAF and appreciable changes in anisotropy and quenching efficiency due to immobilization of the fluorophore head-group in hydrophobic poly(methacrylic acid) domains were observed after binding of the probe at the interface.     

The radiative leptonic decays D^0 \to e^+ e^-\gamma,\mu^+\mu^-\gamma in the standard model and beyond

We present a calculation of the rare decay modes and in the framework of the standard model. For the short distance part we have derived QCD corrections to the Wilson coefficients involved, including C₉. The latter is found to be strongly suppressed by the corrections, leading to diminished values for the branching ratios in the 10^-10 range. Within SM the exclusive decays are dominated by long distance effects. Non-resonant contributions are estimated using heavy quark and chiral symmetries to be at the level of , compared to the contributions arising from , with . The total SM branching ratio is predicted to be in the range (1-. We also consider contributions coming from MSSM with and without R parity conservation. The effects from MSSM are significant only for the R parity violating case. Such contributions enhance the branching ratio to , based on appropriately allowed values for C₉ and C₁₀. This selects as a possible probe of new physics. Received: 25 October 2002 / Published online: 24 January 2003     

Dispersion of nano-silicon carbide (SiC) powder in aqueous suspensions

The dispersion characteristics of nanosize silicon carbide (SiC) suspension were investigated in terms of surface charge, particle size, rheological measurement and adsorption study. Ammonium polycarboxylate has been used as dispersant to stabilize the suspension. It was found that the isoelectric point (iep) of SiC powder was pH_iep (4.9). The surface charge of powder changed significantly in presence of the ammonium polycarboxylate dispersant and iep shifted significantly towards lower acidic pH (3.6). The shift in iep has been quantified in terms of ΔG ⁰ _SP, the specific free energy of adsorption between the surface sites and the adsorbing polyelectrolyte (APC). The values of ΔG ⁰ _SP (−10.85 RT unit) estimated by the electro kinetic data compare well with those obtained from adsorption isotherms (−9.521 RT unit). The experimentally determined optimum concentration of dispersant required for maximizing the dispersion was found to be 2.4 mg/g of SiC (corresponding to an adsorbed amount of 1.10 mg/g), at pH 7.5. This is much below the full monolayer coverage (corresponding to adsorbed amount of 1.75 mg/g) of the particles surface by the dispersant. The surface charge quantity, rheological, pH, electro kinetic and adsorption isotherm results were used to explain and correlate the stability of the nanosize silicon carbide in aqueous media. At pH 7.5, where both SiC surface and APC are negatively charged, the adsorption of APC was low because of limited availability of favourable adsorption sites. In addition, the brush-like configuration of the adsorbed polymer prevented close approach of any additional dispersant; hence stabilization of the slurry happens at a comparatively lower concentration than the monolayer coverage.     

Solvent extraction of Am(III) and Eu(III) from nitrate solution using synergistic mixtures of N-tridentate heterocycles and chlorinated cobalt dicarbollide

The separation by solvent extraction of ²⁴¹Am(III) from ¹⁵²Eu(III), in 1 M NaNO₃ weakly acidic (pH 4) aqueous solutions, into dilute (ca. 10⁻² M) solutions of triazinylbipyridine derivatives (diethylhemi-BTP or di(benzyloxyphenyl)hemi-BTP) and chlorinated cobalt dicarbollide (COSAN) in 1-octanol or nitrobenzene has been studied. The N-tridentate heterocyclic ligands, which are selective for Am(III) over Eu(III), secured efficient separation of the two metal ions, while COSAN, strongly hydrophobic and fully dissociated in polar diluents, enhanced the extraction of the metal ions by ion-pair formation. Molecular interactions between the two co-extractants, observed at higher concentrations, led to the precipitation of their 1: 1 molecular adduct. In spite of that, efficient separations of Am and Eu ions were attained, with high separation factors, SF_Am/Eu of 40 and even 60, provided the concentration of hemi-BTP was significantly greater than that of COSAN. Excess COSAN concentrations caused an antagonistic effect, decreasing both the distribution ratio of the metal ions and their separation factor.     

Pair exchange interaction in a crystalline nitroxide radical ESR study of dimers in the triplet state

The dimerization of the 9-aza-bicyclo (3,3,1) nonan-3-one-9-oxyl in the solid state is investigated by use of ESR spectroscopy. The ESR spectrum of a single crystal is characteristic of symmetric pairs of exchange-coupled radicals in a thermally accessible triplet state. The presence of well-resolved hyperfine structure is evidence for strongly localized excitations with a jumping rate lower than 10⁷ Hz.

The ESR spectrum is well described by the spin hamiltonian

At 35 GHz the observed splitting of the m _s=+ 1?0 transition has been found to be slightly different from that of the m _s=0?-1 one; this anomaly is explained by the mixing of the m _s electronic states.

The parameters and the principal directions of the zero-field splitting, spectroscopic and hyperfine tensors are determined and discussed. The principal directions of the dipolar tensor indicate a nearly equal spin density on the nitrogen and oxygen atoms; from the fine structure parameters D and E, determined to be (-0·0723 ± 0·0005) cm^-1 and (-0·0044±0·0003) cm^-1 at T=293 K respectively, it is suggested that the unpaired electron is partly delocalized on the molecule.

The singlet-triplet energy gap (J) and the zero-field splitting parameters are shown to be linearly temperature-dependent. These variations with temperature are attributed to the thermal expansion of the crystal lattice.     

Universality of sol--gel phase transition of κ-carrageenan in various salts: a steady state fluorescence study

Thermal phase transitions of κ-carrageenan in NaCl, KCl and CaCl₂ solutions were studied using steady state fluorescence (SSF) technique. Pyranine was introduced as a fluorescence probe for studying sol--gel phase transitions. Scattered light, I _sc and fluorescence intensity, I was monitored against temperature to determine the sol--gel (T _sg) phase transition temperatures. It was observed that T _sg values are strongly correlated to NaCl, KCl and CaCl₂ contents. The weight average degree of polymerization, DP _w and gel fraction G, exponents (γ and β) were measured and found to be in accord with the classical Flory--Stockmayer model, i.e., γ and β were found to be close to 1.0, independent of salt content.     

Scattering-parameter measurements of laser diodes

An accurate and simple technique for measuring the input reflection coefficient and the frequency response of semiconductor laser diode chips is proposed and demonstrated. All the packaging parasitics could be obtained accurately using a calibrated probe, and the impedance of the intrinsic diode chip is deduced from the directly measured reflection coefficient. The directly measured impedance of a laser diode is affected strongly by the short bond wire. In the frequency response (S ₂₁) measurements of semiconductor laser diode chips, the test fixture consists of a microwave probe, a submount, and a bond wire. The S-parameters of the probe could be determined using the short-open-match (SOM) method. Both the attenuation and the reflection of the test fixture have a strong influence on the directly measured frequency response, and in our proposed technique, the effect of test fixture is completely removed.     

An Immunonanogold Resonance Scattering-Quenching Probe for Rapid and Sensitive Assay of Microalbumin

A novel and sensitive immunonanogold resonance scattering (RS) spectral probe was obtained for rapid detection of microalbumin (Malb), using 10 nm gold nanaoparticle to label goat anti-human Malb. It was based on that the gold-labeled anti-Malb took place nonspecific aggregation and exhibited a strong RS peak at 577 nm in pH 5.2 C₆H₈O₇–Na₂HPO₄ buffer solution containing polyethylene glycol (PEG), and the immunocomplex formed after specific reaction of gold-labeled anti-Malb with Malb, which led to a decrease in the intensity of RS peak at 577 nm considerably. The decreased RS intensity at 577 nm (ΔI _577nm) was linear to the concentration of Malb in the range of 4–128 ng/mL, with a detection limit of 3.2 ng/mL. The proposed method was applied to detect Malb in healthy human urine samples with satisfactory results.     

Design and Synthesis of a Ruthenium(II) Complex-Based Luminescent Probe for Highly Selective and Sensitive Luminescence Detection of Nitric Oxide

Nitric oxide (NO) is one of the most important intercellular signaling molecules, and plays important roles in various biological systems. In this work, a unique Ru^II complex, tris[(5-(4-methylamino-3-aminobenzylamino)-1,10-phenanthroline)] ruthenium(II) hexafluorophosphate [Ru(MAA-phen)₃][PF₆]₂, has been designed and synthesized as a luminescent probe for the detection of NO in aqueous media. The complex itself is almost non-luminescent, but can specifically react with NO under the aerobic conditions to afford its highly luminescent triazole derivative in aqueous media, [Ru(MTA-phen)₃]²⁺ (MTA-phen: methyl-trazolebenzylamino-1,10-phenanthroline), accompanied by a 302-fold increase in luminescence intensity at 598 nm with a 130 nm Stokes shift. The luminescence response of [Ru(MAA-phen)₃]²⁺ to NO is rapid, highly specific without interferences of other reactive oxygen/nitrogen species, and highly stable against the pH changes in the range of pH 4.5–9.5. These features enable [Ru(MAA-phen)₃]²⁺ to be used as a probe for the highly selective and sensitive luminescence detection of NO in weakly acidic, neutral, and weakly basic media.     

A197Au Mössbauer study of the adsorption of aurocyanide onto activated carbon

The chemical state of gold adsorbed on activated carbon from solutions of KAu(CN)₂ has been studied by¹⁹⁷Au Mössbauer spectroscopy as a function of the pH and concentration of the solution, the loading of the carbon, and the drying conditions of the samples. On freshly prepared specimens Au(CN) ₂ ^? is always the dominant species. Drying leads to the formation of other forms of gold, mainly in samples loaded from strongly acidic media. An oligomeric form of AuCN is, however, also formed when samples loaded at high pH values are dried at temperatures around 100°C.     

pH-Induced Changes in the Secondary Structure of Cytochrome c: an Infrared Spectroscopic Study

The infrared spectra of 3mM solutions of horse heart cytochrome c were recorded as a function of pD(corresponding to acid high spin form, acidic low spin form, native form, lysine form, the so-termed “strained lysine form” as well as the so-termed “A state” of cytochrome c). An analysis of the pH-induced changes in the secondary structure was performed based on changes in the conformation-sensitive amide I bands of this protein. In lysine and strained lysine forms, the contents of random structure increase at the expense of α-helix. In acidic low. spin form (pH4–2.5), cytochrome c was almost unfolded. The proportion of α-helix had a substantial decrease while the contents of both random structure and 3₁₀-helices got a rise. In acidic high spin form (when pH is below 2.5), a further decrease of pD gave no rise to a continued unfolding in cytochrome c but made it refold to the “A state” with properties similar to those of a molten globular state. Adding enough KC1 to the cytochrome c solution(pD2.2 with 0.5MKC1 and pD3.0 with 1.5 MKCl) in which cytochrome c was nearly fully unfolded also led to the formation of A state of cytochrome c. The compositions of all types of secondary structures in A state were evaluated. The behavior of 3₁₀-helices in acidic high/low spin form indicated they might be intermediates between α-helices and random structure in acidic solution as proposed by Miick et al.