Determination of Protoporphyrin IX Disodium Salt Based on Fluorescence Quenching of Glutathione-Capped Cadmium/Tellurium Quantum Dots

ABSTRACT

Aqueous glutathione-capped cadmium/tellurium quantum dots with a diameter of about 3 nm were synthesized. The fluorescence was quenched in the presence of protoporphyrin IX disodium salt, with the excitation wavelength at 320 nm. Under the optimal conditions, the quenched fluorescence intensity was linear in the range of 0.096–16 µg · mL^?1 with a concentration of protoporphyrin IX disodium salt, and the detection limit (3σ) was 2.8 × 10^?2 µg · mL^?1. The proposed method has been applied to the determination of protoporphyrin in serum samples with satisfactory results. The interaction mechanism was investigated.     

Spectroscopic Determination of Cysteine with Alizarin Red S and Copper

ABSTRACT

The interaction between metal complex Cu²⁺–ARS (Alizarin Red S) and l-cysteine was investigated via fluorescence and absorption spectroscopies. In pH 5.2 Britton–Robinson buffer, the addition of L-cysteine into Cu²⁺–ARS system resulted in a fluorescence enhancement because cysteine reduced Cu²⁺ to Cu⁺, which led to Cu²⁺–ARS decompound, and ARS was released. The result was also supported by absorption spectroscopy change. A good linear response of fluorescence intensity as a function of cysteine concentration was obtained ranging from 1.0 × 10^?6 to 4.0 × 10^?5 mol L^?1 with the detection limit as 1.08 × 10^?7 mol L^?1. The introduced method has high selectivity over other amino acids such as cystine, tyrosine, tryptophan, methionine, and glycine. It was applied to determine cysteine in protein hydrolysate of fresh pig blood with recovery of 88.4–100.2%.     

Synthesis and Characterization of New Light Emitter Symmetrical Phenoxazinium Salt and Its Potential Application as Sensor for Assessment of Hg2+

The sensitization of the excited triplet state of a novel symmetrical Bis(dialkylamino)phenoxazinium salt was developed in the presence of Hg²⁺. This effect was used to determine the concentration of Hg²⁺ in different water samples. The phenoxazinium salt sensor was characterized by different spectroscopic tools such as: UV, FTIR, NMR and fluorescence spectra. The sensor has an emission band at 347 nm in DMSO. Hg²⁺ in DMSO at pH 5.6 can remarkably quench the fluorescence intensity of the sensor at 347 nm and a new band was appeared at 436 nm due to the strong complex formation between Hg²⁺ and sensor. The quenching of the band intensity at 347 and the enhancement of the intensity of the new band at 436 were used to determine the Hg²⁺ in different waste water samples. The dynamic range found for the determination of Hg²⁺ concentration is 8.7?×?10^-10 – 1.4?×?10^-6 mol L^?1 with a detection limit of 5.8?×?10^?10 mol L^?1 and quantification detection limit of 1.8?×?10^-9 mol L^-1.     

A Novel Method for the Assessment of Cortisol Hormone in Different Body Fluids Using A New Photo Probe Thiazole Derivative

A low cost and accurate method for the detection and analytical determination of the cortisol in pharmaceutical preparation, blood serum and urine was developed. The method was based upon the enhancement of fluorescence intensity of the band at 424 nm of the photo probe by different cortisol concentrations in acetonitrile at (pH 5.7, λ_ex?=?320 nm). The influence of the different parameters, e.g. pH, solvent, cortisol concentration and foreign ions concentrations that control the enhancement process of fluorescence intensity of the band of photo probe was critically investigated. The remarkable enhancement of the fluorescence intensity at 424 nm in acetonitrile by various concentrations of cortisol was successfully used as a photo- probe for the assessment of cortisol concentration. The calibration plot was achieved over the concentration range 8.0?×?10^?6–5.5?×?10^?9 mol L^?1 cortisol with a correlation coefficient of 0.998 and a detection limit of 4.7?×?10^?9 mol L^?1. The developed method is simple and proceeds without practical artifacts compared to the other determination methods.     

Negative curvature dependent plasmonic coupling and local field enhancement of crescent silver nanostructure

In this contribution, novel luminescent gold nanoclusters were synthesized by utilizing bovine serum albumin as templates with a simple, rapid, and one-pot procedure. The as-prepared gold nanoclusters were highly dispersed in aqueous solution and emitted an intense red fluorescence under UV light (365?nm). They exhibited strong fluorescence and the maximum excitation and emission wavelengths were 480 and 613.5?nm. In addition, the bovine serum albumin-stabilized gold nanoclusters were successfully utilized as novel fluorescent probes for the detection of quercetin for the first time. It was found that the addition of quercetin induced the strong fluorescence intensity of the gold nanoclusters to decrease. The decrease in fluorescence intensity of the gold nanoclusters caused by quercetin allowed the sensitive detection of quercetin in the range of 8.9?×?10^?8?C1.8?×?10^?4?mol?L^?1. The detection limit for quercetin is 1.8?×?10^?8?mol?L^?1 at a signal-to-noise ratio of 3. The present sensor for quercetin detection possessed a low detection limit and wide linear range. In addition, the real samples were analyzed with satisfactory results.     

Study on the Cofluorescence Effect of Europium (III)–Yttrium (III)–Balofloxacin–Sodium Dodecyl Sulfate System and Its Analytical Application

A new fluorescence enhancement phenomenon in the europium(III)–balofloxacin–sodium dodecyl sulfate system was observed when yttrium(III) was added. Based on this, a sensitive cofluorescence assay for the estimation of balofloxacin was established. Under the optimized conditions, the enhanced fluorescence signal was linear over the concentration of balofloxacin ranging from 3.0 × 10^?9 to 7.0 × 10^?6 mol L^?1 with a correlation coefficient of 0.9993. The detection limit (3 σ) was determined as 8.3 × 10^?10 mol L^?1. The presented method was successfully applied to determination of balofloxacin in pharmaceutical preparations, human serum, and urine. The possible fluorescence enhancement mechanism was also discussed.     

A Validated Spectrofluorimetric Method for the Determination of Citalopram in Bulk and Pharmaceutical Preparations Based on the Measurement of the Silver Nanoparticles-Enhanced Fluorescence of Citalopram/Terbium Complexes

A simple, sensitive, and accurate spectrofluorimetric method was developed for the determination of citalopram in bulk and pharmaceutical preparations. The method is based on the enhancement of the weak fluorescence signal (FL) of the Tb (III)-citalopram system in the presence of silver nanoparticles. Fluorescence intensities were measured at 555 nm after excitation at 281 nm. Prepared silver nanoparticles (AgNPs) were characterized by UV-Visible spectra and transmission electron microscopy (TEM). Various factors affecting the formation of citalopram-Tb (III)-AgNPs complexes were studied and optimized. The fluorescence intensity versus concentration plot was linear over the range 0.02–14 μg?mL^?1, with an excellent correlation coefficient of 0.9978. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 7.15?×?10^?6?μg?mL^?1 and 2.38?×?10^?5?μg?mL^?1 respectively. The proposed method was found to have good reproducibility with a relative standard deviation of 3.66 % (n?=?6). The interference effects of common excipients found in pharmaceutical preparations were studied. The developed method was validated statistically by performing recoveries studies and successfully applied for the assay of citalopram in bulk powder and pharmaceutical preparations. Percent recoveries were found to range from 98.98 % to 100.97 % for bulk powder and from 96.57 % to 101.77 % for pharmaceutical preparations.     

Synthesis of 2-Mercaptonicotinic Acid-Capped CdSe Quantum Dots and its Application to Spectrofluorometric Determination of Cr(VI) in Water Samples

The CdSe quantum dots (QDs) capped with 2-mercaptonicotinic acid (H₂MN) were prepared through a controllable process at 80 °C. The prepared QDs were characterized by XRD, TEM, IR, UV–Vis and fluorescence (FL) techniques. It was found that the QDs were nearly mono-disperse with the diameters in the range of 8–10 nm. These QDs are capable to exhibit strong FL even in concentrated acidic media. They exhibit an enhanced fluorescence in the presence of Cr(VI), which was used for the determination of Cr(VI) in water samples. The linear range was found to be 1?×?10^?7–6.0?×?10^?6 M with the RSD and DL of 0.92 % and 5?×?10^?8 M, respectively. Except that Ca²⁺ and Fe³⁺ which can be eliminated through a simple precipitation process, the other co-existent ions present in natural water were not interfered. The recoveries obtained for the added amounts of Cr(VI) were in the range of 96.9–103.2 %, which denote on application of the method, satisfactorily.     

Toxic effects of copper (II) ions on bovine hemoglobin

In this paper, the toxic influence of copper ions (II) on bovine hemoglobin was investigated by the combination of ultraviolet-visible absorption, fluorescence, time-resolved fluorescence, synchronous fluorescence, and circular dichroism spectra. Driven by hydrophobic and electrostatic forces, copper ions (II) could interact with bovine hemoglobin to form bovine hemoglobin-copper ions (II) complex with one binding site. The binding constant (K) was 1.57?×?10⁴, 1.89?×?10⁴ and 2.11?×?10⁴?L/mol at 298, 304, and 310?K, respectively. The binding distance (r) was 4.24?nm. Fluorescence and time-resolved fluorescence spectra showed that bovine hemoglobin quenched by copper ions (II) was a static quenching process. Results of synchronous fluorescence spectra revealed that the microenvironment and the conformation of bovine hemoglobin were changed during the binding reaction. Data of circular dichroism spectra suggested that with the increasing concentration of copper ions (II), the secondary structure of bovine hemoglobin underwent a decrease in α-helix and alteration in backbone microenvironment. Copper ions (II) was thus evidenced to have a certain toxic effect on physical bodies.     

Fluorescence Modulation and Photochromism in Azobismaleimide Derivatives

A fluorophore-photochrome system incorporating an aryleneimine type fluorophore and an azobismaleimide photochrome was developed and the photochemical properties of this system were investigated. The photoisomerization of trans-azoaromatic chromophore leads to the increase of the fluorescence intensity of fluorophore. The cis azobismaleimide isomers revert photochemically to the trans form and the emission intensity decreases. The fluorescence intensity of the imine fluorophore can be modulated under irradiation with UV and visible (436 nm) light due to reversible trans-cis-trans photoisomerization of azobismaleimide partner. The photoisomerization kinetics was obeyed a first-order relationship with a rate constant of 1.95?×?10^?2 s^?1 for azobismaleimide/imine fluorophore system and for polyazothioetherimide/imine derivative the kinetics was described by a biexponential equation.     

Comparative Study on Three Different Systems of Chemiluminescence Flow‐Injection Determination of Leucogen

Abstract

The effects of three systems on the chemiluminescence (CL) intensity have been studied in this paper, such as leucogen–potassium permanganate–rhodamine B, leucogen–cerium (IV)–rhodamine B, and leucogen–luminol–hydrogen peroxide (called system 1, system 2, and system 3, respectively). The mechanism of these reactions is also discussed. Surfactant (CTMAB) has a remarkably sensitive effect on these systems mentioned above. Therefore, three new flow injection chemiluminescence methods for the determination of leucogen have been established. For system 1, the linear range is 8.0×10^?8 to 4.0×10^?5 g mL^?1, with limits of detection 2×10^?8 g mL^?1; the relative standard deviation is 2.5% (n=11, Cs=4.0×10^?6 g mL^?1). For system 2, the linear range is 1.0×10^?8 to 5.0×10^?6 g mL^?1, with limits of detection 3×10^?9 g mL^?1; the relative standard deviation is 5.1% (n=11, Cs=1.0×10^?6 g mL^?1). For system 3, the linear range is 4.0×10^?8 to 2.0×10^?6 g mL^?1, with limits of detection 1×10^?8 g mL^?1; the relative standard deviation is 1.3% (n=11, Cs=1.0×10^?7 g mL^?1). Compared with the three methods above, system 3 is confirmed as the best method. This method has been applied to the determination of leucogen with satisfactory results.     

A New Candidate Laser Dye Based 1,4-Bis[β-(2-Naphthothiazolyle)Vinyl]Benzene. Spectroscopic Behavior,Laser Parameters and Excitation Energy Transfer

A new candidate laser dye based 1,4-bis[β-(2-naphthothisolyl) vinyl] benzene (BNTVB) were prepared, and characterized in various organic solvents. The center polarity is less sensitive than electronic absorption. A red shift was noticed in the fluorescence spectra (ca. 40 nm) with increment in the solvent’s polarity, this means that BNTVB’s polarity appreciates upon excitation. The dipole moment of ground state (μ_g) and the excited singlet state dipole moment (μ_e) are determined from Kawski – Chamma and Bakshiev–Viallet equations using the disparity of Stokes shift with solvent polarity function of ε (dielectric constant) and n (refractive index) of the solvent. The result was found to be 0.019D and 5.13D for ground and exited state, in succession. DFT/TD-DFT manners were used to understand the electronic structures and geometric of BNTVB in other solvents. The experimental and theoretical results showed a good agreement. The photochemical quantum yield (Ф_c) of BNTVB was calculated in variable organic reagents such as Dioxane, CHCl₃, EtOH and MeOH at room temperature. The values of φ_c were calculated as 2.3?×?10^?4, 3.3?×?10^?3, 9.7?×?10^?5 and 6.2?×?10^?5 in Dioxane, CHCl₃, EtOH and MeOH, respectively. The dye solutions (2?×?10^?4 M) in DMF, MeOH and EtOH give laser emission in the blue-green region. The green zone is excited by nitrogen pulse 337.1 nm. The tuning range, gain coefficient (α) and cross – section emission (σ_e) of laser were also estimated. Excitation energy transfer from BNTVB to rhodamine-6G (R6G) and N,N-bis(2,6-dimethyphenyl)-3,4:9,10-perylenebis-(dicarboximide) (BDP) was also studied in EtOH to increase the laser emission output from R6G and BDP when excited by nitrogen laser. The dye-transfer power laser system (ETDL) obeys the Foster Power Transmission (FERT) mechanism with a critical transmission distance, R_o of 40 and 32 ? and k_ET equals 2.6?×?10¹³ and 1.06?×?10¹³ M^?1 s^?1 for BNTVB / R6G and BNTVB / BDP pair, respectively.     

Selective Fluorescence Sensing of Deoxycytidine 5��-Monophosphate (dCMP) Employing a Bis(diphenylphosphate)diimine Ligand

A new bis(diphenylphosphate)diimine ligand (BP1) was prepared and evaluated for its ability for selective detection of deoxycytidine 5??-monophosphate (dCMP). BP1 exhibited off-type fluorescence in the presence of dCMP. The fluorescence of BP1 was significantly quenched upon the addition of 2.5?×?10^?4 M dCMP and the detection limit was 1.25?×?10^?5 M in MeCN-H₂O (1:1, v/v). The binding ratio between BP1 and dCMP was determined to be 1:1 with the binding constant of 3.98?±?0.60?×?10^?3 M^?1.     

Poly(1-amino-5-chloroanthraquinone): Highly Selective and Ultrasensitive Fluorescent Chemosensor For Ferric Ion

Poly(1-amino-5-chloroanthraquinone) (PACA) was firstly synthesized by a chemically oxidative interfacial polymerization. The PACA has been developed as a fluorescent sensor for the determination of Fe(III) in semi-aqueous solution at pH 7.0. The sensor exhibited remarkably high sensitivity toward Fe³⁺ since the fluorescence of the polymer could be significantly quenched even though trace Fe³⁺ was added. The sensor showed a linear fluorescence emission response over a wide concentration range from 1.0?×?10^?10 to 1.0?×?10^?4 M, with an ultra-low detection limit of 2.0?×?10^?11 M. The quenching of the fluorescence was found to be static one due to the formation of non-fluorescent complex in the ground state.     

Interaction Between Isoquercitrin and Bovine Serum Albumin by a Multispectroscopic Method

ABSTRACT

The interaction of isoquercitrin and bovine serum albumin (BSA) was investigated by means of fluorescence spectroscopy (FS), resonance light scattering spectroscopy (RLS), and ultraviolet spectroscopy (UV). The apparent binding constants (K _a) between isoquercitrin and BSA were 5.37 × 10⁵ L mol^?1 (293.15 K) and 2.34 × 10⁵ L mol^?1 (303.15 K), and the binding site values (n) were 1.18 ± 0.03. According to the Förster theory of non-radiation energy transfer, the binding distances (r) between isoquercitrin and BSA were 1.94 and 1.95 nm at 293.15 K and 303.15 K, respectively. The experimental results showed that the isoquercitrin could be inserted into the BSA, quenching the inner fluorescence by forming the isoquercitrin–BSA complex. The addition of increasing isoquercitrin to BSA solution leads to the gradual enhancement in RLS intensity, exhibiting the formation of the aggregate in solution. It was found that both static quenching and non-radiation energy transfer were the main reasons for the fluorescence quenching. The entropy change and enthalpy change were negative, which indicated that the interaction of isoquercitrin and BSA was driven mainly by van der Waals interactions and hydrogen bonds. The process of binding was a spontaneous process in which Gibbs free energy change was negative.     

Flow‐Injection Chemiluminescence Study of Luminol–Hydrogen Peroxide–Carbendazim System

Abstract

A new flow‐injection chemiluminescence (CL) method is described for the determination of carbendazim. The method is based on the CL reaction of luminol and hydrogen peroxide (H₂O₂). Carbendazim can greatly enhance the chemiluminescence intensity in sodium hydroxide–sodium dihydrogen phosphate (NaOH–NaH₂PO₄) medium (pH=12.6). Under the optimum conditions, the linear range for the determination of carbendazim is 2.00×10^?8 to 2.00×10^?6 g mL^?1 with a detection limit (S/N=3) of 7.24×10^?9 g mL^?1. The relative standard deviation is 1.8% for 1.0×10^?7 g mL^?1 carbendazim (n=8). The proposed method has been applied to the determination of carbendazim in tap‐water samples. Furthermore, the possible enhanced CL mechanism is discussed by examining the CL spectra and fluorescence spectra.     

Binding Study of Phenformin with Bovine Serum Album Using a Combined Technique of Equilibrium Dialysis with Flow-Injection Chemiluminescence Detection

ABSTRACT

The interaction between phenformin hydrochloride and bovine serum albumin (BSA) was investigated by the methods of chemiluminescence combined with equilibrium dialysis technique. A novel N-bromosuccinimide (NBS)–eosin Y (EY) chemiluminescence (CL) method was established for the determination of phenformin. The mechanism of this chemiluminescence system was proposed. Optimization studies were performed to determine the phenformin. Under the optimal conditions, the CL intensity was linear for a phenformin concentration over the range of 4.6 × 10^?8 to 5.0 × 10^?5 g/mL. The detection limit was 1.5 × 10^?8 g/mL. The data obtained by the present equilibrium dialysis–CL system were analyzed using the Klotz plot and the Scatchard analysis. The results showed that the Klotz plot and the Scatchard plot are linear with good correlation coefficient, indicating that the phenformin has only one type of binding site on BSA. The binding parameters were the number of the binding sites n (1.02) and the estimated association constant K (2.66 × 10⁴ L/mol). The chemiluminescence system combined with equilibrium dialysis developed in this work demonstrated its use for determination of interaction between drug and protein by using relatively simple instrument.     

A Study on the Permeability of the Triton X-100 Micelles by Fluorescence Decay Kinetics of Probe Molecules

Abstract

The third armonic (355 nm) of a pulsed Nd-YAG laser has been used to excite pyrene in micellar solutions of Triton X-100. Fluorescence quenching by nitromethane and triethylamine of the excited state of pyrene in Triton X-100 has been studied. Quenching rate constant values of 4.94 ± 0.13 × 10⁸M^?1s^?1 and 1.50 ± 0.04 × 10⁸M^?1s^?1 for deactivation by nitromethane and triethylamine, respectively, have been measured. The values obtained are discussed in terms of the interface permeability.     

A highly luminescent complexes of Eu(III) and Tb(III) with norfloxacin and gatifloxacin doped in sol–gel matrix: A comparable approach of using silica doped Tb(III) and Eu(III) as optical sensor

Highly luminescent complexes of Eu and Tb ions with norfloxacin (NFLX) and gatifloxacin (GFLX) were prepared in sol–gel matrix. The red and green emissions of Eu and Tb ions were obtained by the energy transfer from the triplet state of (NFLX) and (GFLX) to the excited emitting states (⁵D₀ and ⁵D₄) of Eu and Tb, respectively. The intensity of the electric field emission bands (⁵D₀→⁷F₂, 617 nm and ⁵D₄→⁷F₅, 545 nm) of Eu and Tb ions were proportional to the concentration of (NFLX at pH 6.0) and (GFLX at pH 3.5) in acetonitrile with excitation wavelengths (λ_ex) (340 and 395) and (370 and 350 nm) for Eu and Tb ions, respectively. The monitored luminescence intensity of the system showed a good linear relationship with the concentration of NFLX within a range of 5×10^?9–5.8×10^?6 and 5×10^?8–1.0×10^?6 mol L^?1 with a correlation coefficient of 0.990, and for GFLX within a range of 2.4×10^?9–3.2×10^?5 and 5×10^?8–8.0×10^?6 mol L^?1 with a correlation coefficient of 0.995. The detection limit (LOD) was determined as 3.0×10^?9 and 1.0×10^?8 mol L^?1 for NFLX and 1.6×10^?10 and 2.0×10^?8mol L^?1 for GFLX. The limit of quantification (LOQ) is 9×10^?9 and 3.0×10^?8 and 4.8×10^?10 and 6.0×10^?8 in case of Eu and Tb, respectively.     

Effects of silicon negative ion implantation in semi-insulating gallium arsenide

ABSTRACT

In the present work, effects of silicon negative ion implantation into semi-insulating gallium arsenide (GaAs) samples with fluences varying between 1?×?10¹⁵ and 4?×?10¹⁷?ions?cm^?2 at 100?keV have been described. Atomic force microscopic images obtained from samples implanted with fluence up to 1?×?10¹⁷?ion?cm^?2 showed the formation of GaAs clusters on the surface of the sample. The shape, size and density of these clusters were found to depend on ion fluence. Whereas sample implanted at higher fluence of 4?×?10¹⁷?ions?cm^?2 showed bump of arbitrary shapes due to cumulative effect of multiple silicon ion impact with GaAs on the same place. GXRD study revealed formation of silicon crystallites in the gallium arsenide sample after implantation. The silicon crystallite size estimated from the full width at half maxima of silicon (111) XRD peak using Debye-Scherrer formula was found to vary between 1.72 and 1.87?nm with respect to ion fluence. Hall measurement revealed the formation of n-type layer in gallium arsenide samples. The current–voltage measurement of the sample implanted with different fluences exhibited the diode like behavior.