Fluorescence Enhancement of the Silver Nanoparticales – Curcumin - Cetyltrimethylammonium Bromide-nucleic Acids System and its Analytical Application

It is found that silver nanoparticles (AgNPs) can further enhance the fluorescence intensity of curcumin (CU) - cetyltrimethylammonium bromide (CTAB) – nucleic acids and improve its anti-photobleaching activity. Under optimum conditions, the enhanced fluorescence intensity is proportion to the concentration of nucleic acids in the range of 2.0 × 10⁻⁸–1.0 × 10⁻⁶ g mL⁻¹ for fish sperm DNA (fsDNA), 2.0 × 10⁻⁸–1.0 × 10⁻⁶ g mL⁻¹ for calf thymus DNA (ctDNA), 1.0 × 10⁻⁸–1.0 × 10⁻⁶ g mL⁻¹ for yeast RNA (yRNA), and their detection limits (S/N = 3) are 8.0 ng mL⁻¹, 10.5 ng mL⁻¹ and 5.8 ng mL⁻¹, respectively. This method is used for determining the concentration of DNA in actual sample with satisfactory results. The interaction mechanism is also studied.     

Study of Enhanced Chemiluminescence of Diperiodatocuprate (III) on 1,10-Phenanthroline/Hydrogen Peroxide/Cetyltrimethylammonium Bromide System

In the paper, a chemiluminescence (CL) system was developed based on the catalytical effect of diperiodatocuprate (III) (DPC) on the 1,10-phenanthroline (phen)/hydrogen peroxide (H₂O₂) in the presence of cetyltrimethylammonium bromide (CTAB). The effects of experimental conditions were investigated. Meanwhile the increase of CL intensity of the DPC/phen/H₂O₂/CTAB system is proportional to the concentration of phen in the range of low concentration. The linear range of the calibration curve is 5.0 × 10⁻⁹–1.0 × 10⁻⁶ mol L⁻¹, and the corresponding detection limit is 1.9 × 10⁻⁹ mol L⁻¹. The effects of phenolic compounds (PCs) on the system were investigated. Hydroquinone was used as an example to investigate the application of the CL system to the determination of PCs. The quenched CL intensity is linearly related to the logarithm of concentration of hydroquinone. The linear range of the calibration curve is 2.5 × 10⁻⁹–1.0 × 10⁻⁵ g mL⁻¹, and the corresponding detection limit is 1.8 × 10⁻⁹ g mL⁻¹. This phen and hydroquinone can be synchronously determined. The method was applied to the determination of hydroquinone in water samples and the recoveries were from 92% to 106%.     

Fluorescence Enhancement Effect for the Determination of Polychlorinated Biphenyls with Bovine Serum Albumin

A sensitive and selective method for the trace determination of 3, 3’, 4, 4’-tetrachlorobiphenyl (PCB77) by using bovine serum albumin (BSA) as a fluorescence probe was introduced. Under optimum conditions, the enhanced fluorescence intensity was proportional to the concentration of polychlorinated biphenyls in the range of 8.9 × 10⁻⁸–5.0 × 10⁻⁶ mol L⁻¹ for PCB77, and 5.0 × 10⁻⁷–5.0 × 10⁻⁶ mol L⁻¹ for 2, 2’, 5, 5’-tetrachlorbiphenyl (PCB52). The detection limits (S/N = 3) of PCB77 and PCB52 were 2.6 × 10⁻⁸ mol L⁻¹ and 2.9 × 10⁻⁷ mol L⁻¹, respectively. Furthermore, the fluorescence enhancement mechanism was discussed in detail. Results indicated that fluorescence enhancement of the system originated from the formation of BSA-PCBs complexes. In addition, PCBs were mainly bound to the tyrosine residues in BSA molecules.     

Spectrofluorimetric Assessment of Doxycycline Hydrochloride in Pharmaceutical Tablets and Serum Sample Based on the Enhancement of the Luminescence Intensity of the Optical Sensor Sm<Superscript>3+</Superscript> Ion

A simple and sensitive spectrofluorimetric method for determination of trace amount of doxycycline hydrochloride (DC) in pharmaceutical tablets and serum samples was developed. In ammonia buffer solution of pH 8.9 the doxycycline hydrochloride can remarkably enhance the luminescence intensity of the Sm³⁺ ion in Sm³⁺- DC complex at λ_ex = 400 nm. The produced luminescence intensity of Sm³⁺- DC complex in DMSO is in proportion to the concentration of DC and used as optical sensor for its determination. The dynamic range for the determination of DC is 1 × 10⁻⁸ – 5 × 10⁻⁶ mol L⁻¹ and in case of quantum yield calculations is 7 × 10⁻⁹ – 5 × 10⁻⁶ mol L⁻¹ with detection limit of 6.5 × 10⁻¹⁰ mol L⁻¹. The enhancement mechanism of the luminescence intensity in the Sm³⁺- DC system has been also discussed. A comparison with other spectrofluorimetric methods for tetracycline derivatives in which Eu³⁺ ion is used instead of Sm³⁺ ion is also studied.     

Spectrofluorimetric Assessment of Chlorzoxazone and Ibuprofen in Pharmaceutical Formulations by using Eu-Tetracycline HCl Optical Sensor Doped in Sol–Gel Matrix

A novel, simple, sensitive and selective spectrofluorimetric method was developed for the determination of trace amounts of chlorzoxazone and Ibuprofen in pharmaceutical tablets using optical sensor Eu-Tetracycline HCl doped in sol–gel matrix. The chlorzoxazone or Ibuprofen can remarkably enhance the luminescence intensity of Eu-Tetracycline HCl complex doped in a sol–gel matrix in dimethylformamide (DMF) at pH 9.7 and 6.3, respectively, λ_ex = 400 nm. The enhancing of luminescence intensity peak of Eu-Tetracycline HCl complex at 617 nm is proportional to the concentration of chlorzoxazone or Ibuprofen a result that suggested profitable application as a simple optical sensor for chlorzoxazone or Ibuprofen assessment. The dynamic ranges found for the determination of chlorzoxazone and Ibuprofen concentration are 5 × 10⁻⁹–1 × 10⁻⁴ and 1 × 10⁻⁸–7 × 10⁻⁵ mol L⁻¹, and the limit of detection (LOD) and quantitation limit of detection (LOQ) are 3.1 × 10⁻¹⁰ , 9.6 × 10⁻¹⁰ and 5.6 × 10⁻¹⁰, 1.7 × 10⁻⁹ mol L⁻¹, respectively.     

Determination of Enoxacin Using Tb Composite Nanoparticles Sensitized Luminescence Method

In our study, terbium-acetylacetone (Tb-acac) composite nanoparticles have been prepared under vigorous ultrasonic irradiation. The nanoparticles are water soluble, stable and have extremely narrow emission bands and high internal quantum efficiencies. They were used as fluorescence probes in the determination of enoxacin (Enox) based on the fluorescence enhancement of nanoparticles through fluorescence resonance energy transfer (FRET). The influence of buffer solution on the fluorescence intensity was investigated. Under the optimum conditions, the fluorescence intensity of the Tb-acac-Enox system is linearly proportional to the Enox concentration in the Enox concentration range of 2 × 10⁻⁷–1 × 10⁻⁴ M. The correlation coefficient for the calibration curve was 0.9976. The limit of detection as defined by IUPAC, C _LOD = 3S _b/m (where S _b is the standard deviation of the blank signals and m is the slope of the calibration graph) was found to be 3 × 10⁻⁸ M. The relative standard deviation (RSD) for six repeated measurements of 1 × 10⁻⁴ M Enox was 1.35%. The method was applied to the determination of Enox in pharmaceutical formulation and recovery results were obtained from urine samples.     

Spectrofluorimetric Assessment of Hydrochlorothiazide Using Optical Sensor Nano-Composite Terbium Ion Doped in Sol-Gel Matrix

A new, simple, sensitive and selective spectrofluorimetric method for the determination of Hydrochlorothiazide was developed in acetonitrile at pH 6.2. The Hydrochlorothiazide can remarkably enhance the luminescence intensity of the Tb³⁺ ion doped in sol–gel matrix at λ_ex = 370 nm. The intensity of the emission band of Tb³⁺ ion doped in sol–gel matrix was increased due to the energy transfer from the triplet excited state of Hydrochlorothiazide to (⁵D₄) excited energy state of Tb³ ion. The enhancement of the emission band of Tb³⁺ ion doped in sol–gel matrix at (⁵D₄→⁷ F₅) 545 nm was directly proportion to the concentration of Hydrochlorothiazide with a dynamic ranges of 5.0 × 10⁻¹⁰—5.0 × 10⁻⁶ mol L⁻¹ and detection limit of 2.2 × 10⁻¹¹ mol L⁻¹.     

Synthesis of Novel Eu(III) Luminescent Probe Based on 9- Acridinecarboxylic Acid Skelton for Sensing of ds-DNA

Eu(III)-9-acridinecarboxylate (9-ACA) complex was synthesized and characterized by elemental analysis, conductivity measurement, IR spectroscopy, thermal analysis, mass spectroscopy, ¹H-NMR, fluorescence and ultraviolet spectra. The results indicated that the composition of this complex is [Eu(III)-(9-ACA)₂(NCS)(C₂H₅OH)₂] 2.5 H₂O and the oxygen of the carbonyl group coordinated to Eu(III). The interaction between the complex with nucleotides guanosine 5′- monophosphate (5′-GMP), adenosine 5′-diphosphates (5′-ADP), inosine (5′-IMP) and CT-DNA was studied by fluorescence spectroscopy. The fluorescence intensity of Eu(III)-9-acridinecarboxylate complex was enhanced with the addition of CT-DNA. The effect of pH values on the fluorescence intensity of Eu(III) complex was investigated. Under experimental conditions, the linear range was 9–50 ng mL⁻¹ for calf thymus DNA (CT- DNA) and the corresponding detection limit was 5 ng mL⁻¹. The results showed that Eu(III)-(9-ACA)₂ complex binds to CT-DNA with stability constant of 2.41 × 10⁴ M .     

Determination of Paracetamol Based on its Quenching Effect on the Photoluminescence of CdTe Fluorescence Probes

L-Cysteine capped CdTe nanoparticles (NPs) were synthesized in aqueous medium, and their application as fluorescence probes in the determination of paracetamol was studied. The L-cysteine capped CdTe NPs were characterized by transmission electron microscopy, X-ray diffraction spectrometry, spectrofluorometry, ultraviolet-visible and Fourier transform infrared spectrometry. Based on the distinct fluorescence quenching of CdTe fluorescence probes in the presence of paracetamol, a simple, rapid and specific method for paracetamol determination was presented. Under optimum conditions, the relative fluorescence intensity of CdTe NPs was linearly proportional to paracetamol concentration from 1.0 × 10⁻⁸ mol/L to 1.6 × 10⁻⁷ mol/L with a detection limit of 4.2 × 10⁻⁹ mol/L. The proposed method was applied to detect paracetamol in commercial tablets with satisfactory results.     

Interaction of Thyroxine with 7 Hydroxycoumarin: A Fluorescence Quenching Study

The interaction between thyroxine hormone and 7 hydroxycoumarin (7HC) was investigated using fluorescence quenching method. The experimental results showed that thyroxine could quench the fluorescence of 7HC by forming the 7HC–thyroxine complex with static quenching. The apparent binding constants (K) between 7HC and thyroxine were determined to be 1.51 × 10⁴ (297 K) and 9.06 × 10³ (310 K). The binding sites (n) 0.98 ± 0.1. The thermodynamic parameters showed that the interaction between 7HC and thyroxine was driven mainly by hydrogen bonding interactions and van der Waals force. Calibration for thyroxine, based on quenching titration data, was linear in the concentration range 2.0 × 10⁻⁸ to 3.0 × 10⁻⁷ mol/l. The relative standard deviation was 2.58% for 2.0 × 10⁻⁷ mol/l thyroxine (n = 4) and the 3σ limit of detection was 3.42 × 10⁻⁸ mol/l in cationic surfactant CTAB medium.     

Preparation and Characterization of CdHgTe Nanoparticles and Their Application on the Determination of Proteins

CdHgTe nanoparticles (NPs) with the emission in the near-infrared regions were prepared in aqueous solution, and were characterized by transmission electron microscopy, X-ray diffraction spectrometry, spectrofluorometry and ultraviolet-visible spectrometry. Based on the fluorescence quenching of CdHgTe NPs in the presence of proteins, a novel method for the determination of proteins with CdHgTe NPs as a near-infrared fluorescence probe was developed. Maximum fluorescence quenching was observed with the excitation and emission wavelengths of 500 and 693 nm, respectively. Under the optimal conditions, the calibration graphs were linear in the range of 0.04 × 10⁻⁶–5.6 × 10⁻⁶ g ml⁻¹ for lysozyme (Lyz) and 0.06 × 10⁻⁶–6.1 × 10⁻⁶ g ml⁻¹ for bovine hemoglobin (BHb), respectively. The limits of detection were 13 ng ml⁻¹ for Lyz and 27 ng ml⁻¹ for BHb, respectively. Four synthetic samples were determined and the results were satisfied.     

Cilostazol determination by the enhancement of the green emission of Tb3+ optical sensor

The efficiency of excited-state interaction between Tb³⁺ and the industrial product Cilostazol (CIL) has been studied in different solvents. High luminescence intensity peak at 545 nm of terbium complex in acetonitrile was obtained. The photophysical properties of the green emissive Tb³⁺ complex have been elucidated, the terbium was used as optical sensor for the assessment of CIL in the pharmaceutical tablets and body fluids at pH 3.1 and λ_ex = 320 nm with a concentration range 1.0 × 10⁻⁹–1.0 × 10⁻⁶ mol L⁻¹ of CIL, correlation coefficient of 0.998 and detection limit of 7.5 × 10⁻¹⁰ mol L⁻¹.     

Investigation on the Micelle-Sensitized Ce (IV) - Lornoxicam-Rh B Chemiluminescence System and its Application

Based on the micelle synergism mechanism, a simple and sensitive flow injection chemiluminescence (FI-CL) method for the assay of lornoxicam was described. The CL signal generated from the reaction of Ce (IV) with lornoxicam in acidic solution was very weak, while the interfusion of sodium dodecyl benzene sulfonate (SDBS) resulted in a highly CL intensity. Under the optimum experimental conditions, the CL intensity was proportional to lornoxicam concentration over the range 1.0 × 10⁻¹⁰–7.3 × 10⁻⁸ g/mL with a detection limit of 4.9 × 10⁻¹¹ g/mL (3σ). The relative standard deviation for 11 replicate measurements of 3.0 × 10⁻⁹ g/mL of lornoxicam was 1.9%. The proposed method was successfully applied for the assay of lornoxicam in pharmaceuticals, human serum and urine with excellent recovery. The possible mechanism of CL reaction was also discussed briefly.     

Determination of Ofloxacin using a Highly Selective Photo Probe Based on the Enhancement of the Luminescence Intensity of Eu3+—Ofloxacin Complex in Pharmaceutical and Serum Samples

A rapid, simple and sensitive spectrofluorimetric method for determination of trace amount of ofloxacin was developed. At pH 5.1 the ofloxacin enhances the luminescence intensity of the Eu³⁺ ion in Eu³⁺- ofloxacin complex at λ_ex = 365 nm. The produced luminescence intensity of Eu³⁺-ofloxacin complex was in proportional to the concentration of ofloxacin. The working range for the determination of ofloxacin was 5.0 × 10^-9–5.0 × 10^-6 mol L^-1 with lower detection limit (LOD) and quantitative detection limit (QDL) of 3 × 10^-9 and 9 × 10^-9 mol L^-1, respectively. The enhancement mechanism of the luminescence intensity in the Eu³⁺-ofloxacin system has been also explained. The method revealed good selectivity for ofloxacin in the presence of coexisting substances and used successfully for the assay of ofloxacin in pharmaceutical preparations and serum. A comparison with other standard methods was also discussed.     

Spectrofluorimetric Assessment of Metoclopramide Hydrochloride Using Terbium Doped in PMMA Matrix Optical Sensor

A new, simple and accurate spectrofluorimetric method for the determination of metoclopramide hydrochloride was developed. The metoclopramide hydrochloride can remarkably enhance the luminescence intensity of the Tb³⁺ ion doped in PMMA matrix at λ_ex = 360 nm in methanol at pH 6.9. The intensity of the emission band at 545 nm of Tb³⁺ ion doped in PMMA matrix is increased due to the energy transfer from metoclopramide hydrochloride to Tb³⁺ in the excited stated. The effect of different parameters, e.g., pH, temperature, Tb³⁺ concentration, foreign ions that control the fluorescence intensity of the produced ion associate was critically investigated. The calibration curve of the emission intensity at 545 nm shows linear response of metoclopramide over a concentration range of 5 × 10⁻⁵–5.0 × 10⁻⁸ M with detection limit of 8.7 × 10⁻¹⁰ M. The method was used successfully for the determination of metoclopramide in pharmaceutical preparations and human serum. The average recovery of 99.48% with standard deviation of 0.32% and 96.98% with standard deviation of 0.4%, of pharmaceutical preparations and human serum respectively, were obtained which compared will with the results obtained from standard LC method of average recovery 99.04% and standard deviation of 0.6% and average recovery of 98.19% with standard deviation of 0.6% of pharmaceutical preparations and human serum, respectively.     

Pyrophosphate Selective Recognition in Aqueous Solution Based on Fluorescence Enhancement of a New Aluminium Complex

A novel and simple fluorescence enhancement method for selective pyrophosphate(PPi) sensing was proposed based on a 1:1 metal complex formation between bis(8-hydroxy quinoline-5-solphonat) chloride aluminum(III) (Al(QS)₂Cl), (L) and PPi in aqueous solution. The linear response range covers a concentration range of 1.6 × 10⁻⁷ to 1.0 × 10⁻⁵ mol/L of PPi and the detection limit of 2.3 × 10⁻⁸ mol/L. The association constant of L-PPi complex was calculated 2.6 × 10⁵ L/mol. L was found to show selectively and sensitively fluorescence enhancement toward PPi over than I₃^-, NO₃^-, CN⁻, CO₃²⁻, Br⁻, Cl⁻, F⁻, H₂PO4⁻ and SO₄²⁻, which was attributed to higher stability of inorganic complex between pyrophosphate and L.     

Spectrofluorimetric Determination of Dopamine Using Chlorosulfonylthenoyltrifluoroacetone–Europium Probe

A new spectrofluorimetric method was developed for the determination of trace amounts of dopamine (DA). Using chlorosulfonylthenoyltrifluoroacetone (CTTA)–europium ion (Eu³⁺) as a fluorescent probe, in a buffer solution at pH = 10.0, DA can remarkably enhance the fluorescence intensity of the CTTA-Eu³⁺ complex at λ = 612 nm; the enhanced fluorescence intensity of Eu³⁺ is proportional to the concentration of DA. Optimum conditions for the determination of DA were also investigated. The linear range and detection limit for the determination of DA were 5.0 × 10⁻⁸∼1.6 × 10⁻⁵ mol/l and 3.2 × 10⁻⁸ mol/l. This method is simple, practical and relatively free of interference from coexisting substances, and can be applied to assess DA in injection and human serum samples with good precision and accuracy.     

Micelle-Enhanced Spectrofluorimetric Method for Determination of Cholesterol-Reducing Drug Ezetimibe in Dosage Forms

A simple and sensitive spectrofluorimetric method was developed for the determination of ezetimibe in its pharmaceutical formulations. The proposed method is based on investigation of the fluorescence spectral behavior of ezetimibe in sodium dodecyl sulfate (SDS) micellar system. In aqueous solution of acetate buffer pH 5.0, the fluorescence intensity of ezetimibe was greatly enhanced, 200% enhancement, in the presence of SDS. The fluorescence intensity of ezetimibe was measured at 380 nm after excitation at 268 nm. The fluorescence-concentration plot was rectilinear over the range of 0.03–3.0 μg/mL with lower detection limit of 3.08 × 10⁻³ μg/mL. The method was successfully applied to the analysis of ezetimibe in its commercial tablets; the results were in good agreement with those obtained with the reported method. The application of the proposed method was extended to the stability studies of ezetimibe after exposure to different forced degradation conditions, such as acidic, alkaline, photo and oxidative conditions, according to ICH guidelines.     

Interaction of a New Fluorescent Probe with DNA and its Use in Determination of DNA

In this paper we reported a metal complex 1-Zn (2,5-di-[2-(3,5-bis(2-pyridylmethyl)amine-4-hydroxy-phenyl)-ethylene]-pyrazine-Zn) as a fluorescent probe sensing DNA. The result of the competitive experiment of the probe with ethidium bromide (EB) to bind DNA, absorption spectral change and polarization change in the presence and absence of DNA revealed that interaction between the probe and DNA was via intercalation. Ionic strength experiment showed the existence of electrostatic interaction as well. Scatchard plots also confirmed the combined binding modes. The fluorescence enhancement of the probe was ascribed to highly hydrophobic environment when it bound the macromolecules such as DNA, RNA or denatured DNA. The binding constant between the probe and DNA was estimated as 3.13 × 10⁷ mol⁻¹ L. The emission intensity increase was proportional to the concentration of DNA. Based on this, the probe was used to determine the concentration of calf thymus DNA (ct-DNA). The corresponding linear response ranged from 2.50 × 10⁻⁷ to 4.75 × 10⁻⁶ mol L⁻¹, and detection limit was 1.93 × 10⁻⁸ mol L⁻¹ for ct-DNA.