Silver Nanoparticle Based Analysis of Aminoglycosides

Colorimetric silver nanoparticle sensor was developed for determination of aminoglycosides in milk. Silver nanoparticles were synthesized by using sodium borohydride as reducing agent and sodium dodecyl sulfate as stabilizer. Yellow color of silver turned into orange and red in proportion to the concentrations of analytes. Quantitative analyses were performed by using decrease in absorbance of silver nanoparticles at 394 nm. Linear ranges were 20–60 ng mL^?1, 23–60 ng mL^?1, and 60–100 ng mL^?1 for gentamicin, tobramycin, and amikacin, respectively. The method was optimized in terms of pH, ionic strength, and time. This simple and validated method was applied to milk samples and pharmaceutical preparations.     

Study on the Fluorescence Quenching Reaction of Amitriptyline and Clomipramine Hydrochlorides with Eosin Y and its Analytical Application

Amitriptyline.HCl (AMI) and clomipramine.HCl (CMI) react with eosin Y (EY) in pH 3.8 NaAc-AcH buffer solution to form ion association complex which results in quenching of fluorescence of EY and appearance of a new resonance Rayleigh scattering (RSS) spectrum at 620 nm. The spectral characteristics of absorption, fluorescence and RSS spectra have been investigated. The factors influencing the reaction were studied and optimum conditions for the reaction have been determined. Based on fluorescence quenching, a simple and sensitive spectrofluorimetric method for determination of AMI and CMI has been developed. The fluorescence quenching intensity was measured at 550 nm using an excitation wavelength of 310 nm. The calibration graph was found to be rectilinear in the range 0.08–2.0 μg?mL^?1 with detection limit of 0.017 μg?mL^?1 for AMI and 0.06–2.0 μg?mL^?1 with detection limit of 0.015 μg?mL^?1 for CMI. The method can be satisfactorily applied to the determination of AMI and CMI in tablets without interference from commonly occurring exicipients. The recovery and RSD values obtained indicate good accuracy and precision of the method. The mechanism of the reaction and fluorescence quenching has also been discussed.     

Novel Comparative Synchronous Spectrofluorimetric Study of Benzo(a)pyrene Using Beta-Cyclodextrin and Calix(8)arene as Fluorescence Enhancers

Successfully benzo(a)pyrene could be quantitified in environmental samples by a novel synchronous spectrofluorimetric techniques at a constant wavelength difference Δλ?=?120 nm, using beta-cyclodextrin ‘β-CD’ and calix(8)arene as fluorescence enhancers, where a linear calibration curve was obtained in a concentration range of 900–14,400 pg mL^?1 and 18–360 pg mL^?1 and the detection limit of 380.00 pg mL^?1 and 12.08 pg mL^?1 (which is well below the maximum contaminant concentration for benzo(a)pyrene set by the Environmental Protection Agency ‘EPA’) using both enhancers, respectively. The method can be easily adopted for determination of benzo(a)pyrene in aqueous media including tap water, river water and complex water samples. The recoveries obtained were 85.13–113.36 % with RSD?<?4 %. The proposed method was validated according to International Conference of Harmonization (ICH) guide lines and successfully applied to determine benzo(a)pyrene in pure form and in water samples including contaminated environmental water samples. All the results obtained were compared with those of a published method, where no significant difference was observed.     

Fluorimetric Method Based on Diazotization-Coupling Reaction for Determination of Clenbuterol

A novel fluorimetric method based on diazotization-coupling reaction (DCR) for the determination of clenbuterol is described. In acidic solution, clenbuterol was first diazotized with sodium nitrite, followed by coupling with bisphenol A to produce an azo-compound in NH₃- NH₄Cl buffer. It has found the diazotized clenbuterol- bisphenol A- NH₃- NH₄Cl (DCBN) system has strong fluorescence efficiency compare with the bisphenol A solution. There is a linear relationship between the increased intensity of the fluorescence emission spectra (λ_ex/λ_em?=?276 nm/306 nm) and the concentration of clenbuterol. The effects of the amount of sodium nitrite, diazo reaction time, the amount of bisphenol A, coupling reaction time and coupling reaction temperature have been examined. Under the optional conditions, clenbuterol can be determined over the concentration range of 0.02 to 2.0 μg mL^?1 with a correlation coefficient of 0.9953. The detection limit is 0.01 μg mL^?1 at a signal-to-noise ratio of 3. The relative standard deviation (RSD) for 11 repetitive determinations of 0.9 μg mL^?1 clenbuterol is 0.22 %. The utility of this method was demonstrated by determining clenbuterol in meat samples.     

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.     

Sensitive Fluorescence Detection of Etimicin Based on Derivatives of Formaldehyde and Acetylacetone

A novel fluorescence method for the determination of etimicin is described. Etimicin reacts with acetylacetone and formaldehyde in pH 4.0 Britton-Robinson (B.R.) buffer solution to from a fluorescent substance [I]. Emission spectra of [I] and the reagent blank were overlapped, so the arithmetic emission spectra of the fluorescent substance were obtained by subtracted form the spectra of [I] to the spectra of the reagent blank using the Fluorescence Data Software. There is a linear relationship between the intensity of the arithmetic emission spectra and the concentration of etimicin. Effects of pH, amount of acetylacetone-formaldehyde, and heating time on the determination of etimicin have been examined. Etimicin can be determined over the concentration range of 1.0 to 10.0 μg?mL^?1 with a correlation coefficient of 0.9991. The relative standard deviation (RSD) for 11 repetitive determinations of 5.0 μg?mL^?1 etimicin is 0.22 %. The utility of this method was demonstrated by determining etimicin in commercial samples.     

Effect of MeV electron irradiation on the free volume of polyimide

The free volume of the microvoids in the polyimide samples, irradiated with 6 MeV electrons, was measured by the positron annihilation technique. The free volume initially decreased the virgin value from ～13.70 to ～10.98 Å³ and then increased to ～18.11 Å³ with increasing the electron fluence, over the range of 5?×?10¹⁴ – 5?×?10¹⁵ e/cm². The evolution of gaseous species from the polyimide during electron irradiation was confirmed by the residual gas analysis technique. The polyimide samples irradiated with 6 MeV electrons in AgNO₃ solution were studied with the Rutherford back scattering technique. The diffusion of silver in these polyimide samples was observed for fluences >2?×?10¹⁵ e/cm², at which microvoids of size ≥3 Å are produced. Silver atoms did not diffuse in the polyimide samples, which were first irradiated with electrons and then immersed in AgNO₃ solution. These results indicate that during electron irradiation, the microvoids with size ≥3 Å were retained in the surface region through which silver atoms of size ～2.88 Å could diffuse into the polyimide. The average depth of diffusion of silver atoms in the polyimide was ～2.5 μm.     

Determination of Protein by Fluorescence Enhancement of Curcumin in Lanthanum-Curcumin-Sodium Dodecyl Benzene Sulfonate-Protein System

We found that the fluorescence intensity of the lanthanum (La³⁺)-curcumin (CU) complex can be highly enhanced by proteins in the presence of sodium dodecyl benzene sulphonate (SDBS). Based on this finding, a new fluorimetric method for the determination of protein was developed. Under optimized conditions, the enhanced intensities of fluorescence are quantitatively in proportion to the concentrations of proteins in the range 0.0080?C20.0 ??g·mL^?1 for bovine serum albumin (BSA) and 0.00080?C20.0 ??g·mL^?1 for human serum albumin (HSA) with excitation of 425 nm, and 0.00020?C20.0 ??g·mL^?1 for bovine serum albumin (BSA) and 0.00080?C20.0 ??g·mL^?1for human serum albumin (HSA) with excitation of 280 nm, while corresponding qualitative detection limits (S/N????3) are as low as 5.368, 0.573, 0.049, 0.562 µg·mL^?1, respectively. Study on reaction mechanism reveals that proteins can bind with La³⁺, CU and SDBS through self-assembling function with electrostatic attraction, hydrogen bonding, hydrophobic interaction and van der Waals forces, etc. The proteins form a supermolecular association with multilayer structure, in which La³⁺-CU is clamped between BSA and SDBS. The unique high fluorescence enhancement of CU is resulted through synergic effects of favorable hydrophobic microenvironment provided by BSA and SDBS, and efficient intermolecular energy transfer among BSA, SDBS and CU. In energy transfer process, La³⁺ plays a crucial role because it not only shortens the distance between SDBS and CU, but also acts as a ??bridge?? for transferring the energy from BSA to CU.     

A sensitive amperometric detection of dopamine agonist drug pramipexole at functionalized multi-walled carbon nanotubes (f-MWCNTs) modified electrode

The electrochemical detection of dopaminergic agonist drug pramipexole dihydrochloride monohydrate (PPX) has been investigated by cyclic voltammetric (CV) and amperometric i–t techniques at functionalized multi-walled carbon nanotubes-modified glassy carbon electrode. For the first time, a sensitive and rapid electrochemical method was developed for the determination of PPX. The surface morphological characteristics of the proposed electrode have been studied by using transmission electron microscopy (TEM); further, electrochemical impedance spectroscopy (EIS) and Fourier transform infrared spectroscopy (FTIR) have been employed. PPX shows an irreversible anodic peak, which may be ascribed to the oxidation of the –NH groups of PPX. The proposed method was showing good sensitivity of 0.993 μA μM^?1 cm^?2 with a linear range of 5 to 340 μM by amperometric i–t and CV technique shows a linear range of 12.5 to 313 μM with a sensitivity of 1.92 μA μM^?1 cm^?2. The recovery of PPX from blood serum samples was found 100.6 and 98.9 %, respectively. Furthermore, the proposed method has been demonstrated for the determination of PPX in commercially available pharmaceutical samples and good agreement of results obtained.     

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.     

Spectrofluorimetric Protocol for Ceftriaxone in Commercial Formulation and Human Plasma After Condensation with Formaldehyde and Ethyl Acetoacetate

A new spectrofluorimetric method has been developed and validated for the quantification of ceftriaxone in bulk powder, pharmaceutical formulations and spiked human plasma. The developed method is reproducible, accurate, sensitive and cost effective. In this method, ceftriaxone was converted into a fluorescent compound by reacting with 0.8 M ethyl acetoacetate and 25% formaldehyde in a buffered medium (pH = 4.2) at 90 °C. The excitation and emission wavelengths of the fluorescent reaction product are 316 nm and 388 nm respectively. Optimization of the experimental conditions affecting the condensation reaction were carefully carried out and the optimum experimental conditions were incorporated in the procedure. The developed method has a broad linear range (0.2–20 μg mL⁻¹) with a correlation coefficient of 0.9992. The limit of detection (LOD) and limit of quantification (LOQ) was found to be 1.94 × 10⁻² μg mL⁻¹ and 6.47 × 10⁻² μg mL⁻¹ respectively. The common excipients and co-administered drugs were investigated for their interferences effect in the assay. The developed method was validated statistically through recovery studies and successfully applied to ceftriaxone determination in bulk powder, pharmaceutical formulations and spiked human plasma samples. The percent recoveries were found to be in the range of 99.04–100.26% for bulk powder, 98.88–99.92% for pharmaceutical formulations and 94.22–98.48% for spiked human plasma. The results were verified by comparing with reference literature HPLC method and were found in good agreement.     

Determination of Silver by Chemical Vapor Generation with In Situ Trapping Flame Atomic Absorption Spectrometry

ABSTRACT

The hyphenation of chemical vapor generation with an integrated atom trap system for flame atomic absorption spectrometry (CVG-IAT-FAAS) was evaluated for determination of silver in real samples (coal fly ash, sediment, and nickel alloy). The volatile species of silver were formed by reaction with sodium tetrahydroborate(III) in the presence of nitric acid. A new CVG-IAT-FAAS design (versus a water-cooled single silica tube, double-slotted quartz tube) significantly improved the sensitivity and detection limits compared with conventional flame atomic absorption spectrometry (FAAS) for determination of silver. The concentration limit of detection was 0.7 ng mL^?1 for Ag. The overall efficiency of the vapor generation process was estimated to be ca. 12%. For a 2 min in situ preconcentration time, sensitivity was enhanced 143-fold for Ag using the vapor generation atom trapping technique, compared to conventional FAAS. Sensitivity can be further improved by increasing the collection time. The precision of measurement at 10 ng mL^?1 of Ag was 10% RSD. The accuracy of this method was validated by analyses of NRC GBW 07302 (Stream Sediment), BCS CRM No. 346 (Nickel Alloy), NIST SRM 2710 (Montana Soil), NRCC LUTS-1 (Lobster Hepatopancreas), and NIST SRM 1643e (Trace Element in Water) certified reference materials. The measured Ag contents in these five reference materials were in satisfactory agreement with the certified values (spanning the range of 0.066–35 µg g^?1).     

Novel Method for Determination of Anthracene by Coupling Dispersive Liquid-Liquid Extraction to First-Derivative Synchronous Spectrofluorimetry

A novel method could be adopted successfully for determination of anthracene in environmental samples, utilizing dispersive liquid-liquid extraction followed by first-derivative synchronous fluorimetry at a constant wavelength difference Δλ?=?165 nm, where a linear calibration curve was obtained in a concentration range of 0.5–100 ng mL^?1 at 244 nm. The detection limit was 0.1 ng mL^?1. The method can be easily adopted for determination of anthracene in aqueous media including tap water and river water. The recoveries obtained were 85.40–108.02 %. The proposed method was validated according to International Conference of Harmonization (ICH) guide lines and successfully applied to determine anthracene in pure form and in water samples including real life water samples from different sources. All the results obtained were compared with those of published method, where no a significant difference was observed.     

The Mineral Content of Rhizona cyperi after Microwave-Assisted Digestion and Determination by AAS

ABSTRACT

Rhizoma cyperi (tuberal part of Cyperus rotundus Linn) obtained from 15 different zones of China was studied to determine the contents of 16 trace elements such as 4 minor (Ca, K, Mg, and Na), 9 trace (Co, Cr, Cu, Fe, Mn, Mo, Ni, V, and Zn), and 3 toxic (Ag, Cd, and Pb) elements. The concentration determination of 16 elements was performed by atomic absorption spectrophotometry (AAS) after microwave-assisted digestion. A microwave-assisted digestion procedure based on the mixture nitric acid–hydrogen peroxide was evaluated. The method was successfully validated with the good recoveries (97–105%) against CRM GBW07603 (bush twigs and leaves). The calibration curve furnished good linear correlation coefficients (r = 0.9956–0.9999), excellent recoveries (99.35–103.7%), and limits of detection (LOD = 1–50 ng·mL^?1) suitable to determine in Rhizoma cyperi. The results showed that K, Ca, Mg, and Na were the most abundant of the major elements in Rhizoma cyperi with average concentrations of K, 26,221 µg·g^?1; Ca, 1097 µg·g^?1; Mg, 714 µg·g^?1, and Na, 293 µg·g^?1, respectively. K element was determined for the first time in this plant.     

Preparation and comparative structural properties of porous SnO2 microrods and submicrorods

A facile two-step approach has been used for the synthesis of porous SnO₂ rods: the initial room-temperature precipitation of precursor SnC₂O₄ and its subsequent thermal decomposition at 550 °C. Both the as-obtained porous SnO₂ microrods (length ～10.0?±?3.5 μm, diameter ～1.1?±?0.4 μm) and submicrorods (length ～5.8?±?1.9 μm, diameter ～0.4?±?0.1 μm) are the crystalline mixtures of major tetragonal and minor orthorhombic crystal phases, showing a tetragonal fraction of 84.7 and 87.0 %, respectively. When applied as a lithium-ion battery anode, the porous submicrorods (specific surface area ～13.6 m² g^?1) can deliver an initial discharge capacity of 1,730.7 mAh g^?1 with a high coulombic efficiency of 61.6 % and show the 50th discharge capacity of 662.8 mAh g^?1 at 160 mA g^?1 within a narrow potential range of 10.0 mV to 2.0 V. Similarly, even the anode of porous microrods (specific surface area ～11.8 m² g^?1) can still exhibit an initial discharge capacity of 1,661.1 mAh g^?1 at 160 mA g^?1 with a coulombic efficiency of 60.9 %. Regardless of the polymorphic nature, the acquired porosity may only alleviate the huge volume change of anodes for the first cycle; thus, the structural parameters of average size and specific surface area can be feasibly associated with the enhanced lithium storage capability. Anyway, these indicate a facile oxalate precursor method for the controlling synthesis and high performance of rodlike SnO₂ for lithium-ion batteries.     

Sensitive and selective electrochemical sensor for magnolol based on the enhancement effect of multiwalled carbon nanotubes

Herein, insoluble multiwalled carbon nanotubes (MWNTs) were dispersed into N,N-dimethylformamide (DMF) via ultrasonication, resulting in a stable and homogeneous MWNTs suspension. After evaporation of DMF, the surface of glassy carbon electrode was successfully coated with MWNTs film, as confirmed from scanning electron microscopy measurements. In pH 7 phosphate buffer, an irreversible oxidation peak was observed for magnolol, and the peak currents greatly increased on MWNTs film surface. The influences of pH value, amount of MWNTs and accumulation conditions were studied. Based on the remarkable enhancement effect of MWNTs, a new electrochemical sensor with high sensitivity was developed for magnolol. The linear range was from 5 μg?L^?1 to 1 mg?L^?1, and the detection limit was 2 μg?L^?1 (7.51?×?10^?9?M) after a 3-min accumulation. This novel sensor was successfully used to detect the content of magnolol in Chinese traditional medicines, and the recovery was over the range from 98.1 to 99.1 %.     

Sensitive Synchronous Spectrofluorimetric Study of Certain Sunscreens Using Fluorescence Enhancers in Cosmeceutical Formulations

Synchronous spectrofluorimetric methods could be successfully adopted for simultaneous determination of Octinoxate (OMC), Avobenzone (AVO), Octyltriazone (OT), and Phenyl benzimidazole sulfonic acid (PBSA) in moisturizing sunscreen lotion, utilizing β-CD as fluorescence enhancer, and determination of Avobenzone (AVO), Homosalate, Tinosorb M and Phenyl benzimidazole sulfonic acid (PBSA) in presence of Octocrylene (OCR) in whitening sunscreen cream, using micellar medium of Sodium Dodecyl Sulfate (SDS) to enhance fluorescence intensity. For first product, zero order synchronous spectrofluorimetric method was used for determination of OMC and AVO, and derivative synchronous spectrofluorimetric technique was utilized for OT and PBSA in quaternary mixture. Linear calibration curves were obtained in a concentration range of 0.5–8 μg mL^??1 for OMC and AVO, and in range of 0.05–3 μg mL^??1 for OT and 0.001–5 μg mL^??1 for PBSA, by measuring the fluorescence at 370, 405, 333.2 and 340.6 nm, respectively. For second product, first derivative synchronous fluorescence method was used for each UV-filter. A linear calibration curves were obtained in a concentration range of 0.5–8 μg mL^??1 for AVO, in range of 0.1–8 μg mL^??1 for Homosalate, 2–10 μg mL^??1 for Tinosorb M and 0.001–5 μg mL^??1 for PBSA, by measuring the fluorescence at 409.8, 373, 307.2 and 316.8 nm, respectively. The detection limits are well below the maximum admissible concentration. The proposed methods were validated according to ICH guidelines and successfully applied to determine sunscreens in pure form and in Cosmeceutical formulations. All the results obtained were compared with those of published methods, where no significant difference was observed.     

Flow Injection Kinetic Spectrophotometric Determination of Cerium Based on the Decolorization Reaction Between Arsenazo III and Cerium (IV)

ABSTRACT

Trace amounts of cerium were analyzed by flow injection kinetic spectrophotometry, based on the decolorization reaction between arsenazo III and Ce(IV) in sulfuric acid medium at room temperature. The absorbance difference (ΔA) of decolorization was linear with the concentration of Ce(IV). The flow injection technique was used to precisely control the timing. Under the optimum conditions, the determination of Ce(IV) in the range 0.0–8.0 µg mL^?1 with a correlation coefficient (r) of 0.9982, the regression equation was ΔA = 0.0014 + 0.0406c (µg mL^?1). The detection limit (3σ) of 0.2 µg mL^?1 was achieved at a sampling frequency of 60 h^?1. The proposed method was applied to the analyses of Ce in soil successfully.     

Sensitive Chemiluminescence Assay for Patulin in Apple Juice by Flow Injection

Abstract

A sensitive chemiluminescence (CL) procedure for the determination of patulin by flow injection is described. It was found that patulin inhibits the CL generated from the luminol–dissolved oxygen system significantly. The decrement of chemiluminescence intensity was linear with the patulin concentration over the range from 0.04 to 10.0 ng mL^?1 with a detection limit of 0.01 ng mL^?1 (3σ_noise). At a flow rate of 2.0 mL min^?1, a complete analytical process could be performed within 0.5 min, including sampling and washing, with a relative standard deviation of less than 3.0% (n=5). The proposed method was applied successfully in the determination of patulin in apple juice, and the recovery was between 96.9% and 103.9%.     

Measurements of CO2 in a multipass cell and in a hollow-core photonic bandgap fiber at 2 μm

Recently, hollow-core photonic bandgap fibers (HC-PBFs) for use in the 2 μm wavelength region have become available. We have employed tunable diode laser absorption spectroscopy (TDLAS) to quantify CO₂ in nitrogen, injected into a HC-PBF. Our spectrometer contains both an HC-PBF-based absorption cell and an astigmatic Herriott multipass gas cell. The Herriott cell was used for comparison with the HC-PBF cell. The HC-PBF cell’s sensitivity and limit of detection were calculated to be 3.5×10^?4 cm^?1?Hz^?1/2 and 59 ppm?m, respectively. To substantiate the spectrometer performance, a measurement was done in the Herriott cell probing a reference gas mixture with nominal 400 μmol/mol CO₂ in N₂. The spectrometric results were in good agreement with the reference value. The relative standard uncertainty of the spectrometric result was found to be at the ±2 % level.