共振非线性散射技术测定盐酸普鲁卡因与β-环湖精包结常数的新方法

盐酸普鲁卡因水溶液的共振非线性散射较弱，当β环糊精加人溶液中并与盐酸 普鲁片因形成包合物时，共振非线散射强度明显增强，且随着β-环糊精的浓度增 加，体系的共振非线性散射逐渐增强，利用共振非线性散射技术研究糊精与盐酸普 鲁卡因的相互作用，并发展了一种用二级散射、二倍频散射、三倍频散射和3／2倍 频散射技术测定β-包合物包结常数的新方法，测定结果与用分光光度法、荧光法 和共振瑞利散射法测得结果一致，从而建立起测定环糊精包结常数的新方法．     

A new method for the determination of the critical micelle concentration of Triton X-100 in the absence and presence of beta-cyclodextrin by resonance Rayleigh scattering technology

A new method for the determination of the critical micelle concentration (CMC) of Triton X-100 in aqueous solution and beta-cyclodextrin solution by resonance Rayleigh scattering (RRS) has been developed. The method is based on the measurement of the RRS intensity of different concentration of Triton X-100 in aqueous solution and beta-cyclodextrin solution (6.0 x 10(-4) mol l(-1)). When the RRS intensities were plotted against the concentration of Triton X-100, an inflection point appeared at the Triton X-100 concentration of 5.0 x 10(-4) mol l(-1) in aqueous solution and 1.1 x 10(-3) mol l(-1) in beta-cyclodextrin solution, respectively. These values of concentration corresponded to the CMC of Triton X-100 in aqueous solution and beta-cyclodextrin solution, which also agreed closely with the results reported by surface tension and UV-Vis absorption spectrophotometry. Therefore, the present RRS method is very convenient, rapid and accurate and can be used as a new technology for the determination of CMC values of surfactants without any probe. The relationship between the RRS intensity and the concentration, aggregate state and the aggregate molecular size of Triton X-100 has been primarily discussed.     

Determination of trace procaine hydrochloride by differential pulse adsorptive stripping voltammetry with a Nafion modified glassy carbon electrode.

A sensitive and selective method for the determination of procaine hydrochloride with a Nafion-modified glassy carbon electrode has been developed. The voltammetric behavior of procaine hydrochloride on the Nafion-modified electrode indicated that the modified electrode not only increased the sensitivity of the determination of procaine hydrochloride, but also catalyzed the electrode process. Procaine hydrochloride was accumulated in Britton-Robinson buffer (pH 2.09) at a potential of -0.2 V (vs. SCE) for 180 s, and was then determined by differential pulse adsorptive stripping voltammetry. The effect of various parameters, such as the pH of the medium, the mass of drop-coated Nafion, the accumulation potential, the accumulation time and the scan rate, were investigated. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 6.0 x 10(-8) to 6.0 x 10(-6) mol l(-1) with a correlation coefficient of 0.9987. The relative standard deviation was 4.18% for eight successive determinations of 1.0 x 10(-7) mol l(-1) procaine hydrochloride, and the detection limit (three times signal to noise) was 7.0 x 10(-9) mol l(-1). A study of interfering substances was also performed, and the method was applied to the direct determinations of procaine hydrochloride in the injection solution of procaine hydrochloride and in rabbit serum.     

Spectroscopic study of orange G-beta-cyclodextrin complex and its analytical application

The mechanism of the inclusion of orange G and beta-cyclodextrin (beta-CD) has been studied by using both spectrophotometry and infrared spectroscopy. Effects of the pH, concentrations of beta-CD, and ionic strength on the inclusion complex of beta-CD and orange G were examined. The result showed that orange G reacts with beta-CD to form a 1:1 host-guest complex with an apparent formation constant of 3.03 x 10(3)mol(-1)l. The thermodynamic parameters of inclusion complex, DeltaG(0), DeltaH(0), and DeltaS(0) were obtained. Based on the enhancement of the absorbance of orange G produced through complex formation, a ratiometric method spectrophotometrically for the determination of orange G in bulk aqueous solution in the presence of beta-CD was developed, which overcome the effect of condition change on the determination of orange G. The linear relationship between the absorbance and orange G concentration was obtained in the range of 1.0 x 10(-5) to 4.0 x 10(-5)mol l(-1), with a correlation coefficient of 0.9998. The detection limit was 3.6 x 10(-6)mol l(-1). The principal advantage of the proposed method is high accuracy because ratiometry was used in measurement.     

Determination of the binding constant for the inclusion complex between procaine hydrochloride and beta-cyclodextrin by capillary electrophoresis

The apparent electrophoretic mobilities of procaine hydrochloride (μ_i) in a series of concentration of β-cyclodextrin were measured directly by capillary electrophoresis technology. A new mathematical treatment method is proposed, which based on the fact that the molar ratio of the inclusion complex was 1:1 established by spectrophotometry. Using the proposed method, the binding constant of the inclusion complex of procaine hydrochloride with β-cyclodextrin can be obtained easily. The determination result was in correspondence with those of the spectrophotometric and fluorescence methods.     

The fluorescence study of the inclusion coordinated compound of beta-cyclodextrin and p-hydroxyphenolacetamide and its analytical applications

The inclusion coordinated compound fluorescence of p-hydroxyphenolacetamide (PHPA) with beta-cyclodextrin was studied and a high sensitive analytical method to determine the content of PHPA was established based on the increased fluorescence intensity of the coordinated compounds in Britton-Robinson buffer solution (pH 7). The wavelength of the excited emission are 282 and 310 nm, respectively. The enhanced coordinated compounds fluorescence intensity is proportional to the concentration of PHPA in the range 0.030-11.0 mg/l. The relative standard deviation (R.S.D.) were within 0.66-4.2%. Correlation coefficient and inclusion binding constant Kf are obtained within 0.9950-0.9996 and 4.67 x 10(2), respectively. Meanwhile, a linear increase of the resonance light scattering (RLS) with the inclusion coordinated compounds concentration was noticed at a synchronous wavelength of 584 nm. The forming reasons of inclusion coordinated compounds were investigated. The 1:1 molar ratio composition of inclusion compound was measured with DTA and elemental analysis. The method is simple, rapid and has a good reproducibility. The method was used for determination of PHPA in an artificial sample with satisfactory results.     

Spectrophotometric determination of fluoxetine by batch and flow injection methods

A rapid, simple, and accurate spectrophotometric method is presented for the determination of fluoxetine by batch and flow injection analysis methods. The method is based on fluoxetine competitive complexation reaction with phenolphthalein-beta-cyclodextrin (PHP-beta-CD) inclusion complex. The increase in the absorbance of the solution at 554 nm by the addition of fluoxetine was measured. The formation constant for fluoxetin-beta-CD was calculated by non-linear least squares fitting. Fluoxetine can be determined in the range 7.0 x 10(-6)-2.4 x 10(-4) mol l(-1) and 5.0 x 10(-5)-1.0 x 10(-2) mol l(-1) by batch and flow methods, respectively. The limit of detection and limit of quantification were respectively 4.13 x 10(-6) mol l(-1) and 1.38 x 10(-5) mol l(-1) for batch and 2.46 x 10(-5) mol l(-1) and 8.22 x 10(-5) mol l(-1) for flow method. The sampling rate in flow injection analysis method was 80+/-5 samples h(-1). The method was applied to the determination of fluoxetine in pharmaceutical formulations and after addition to human urine samples.     

beta-Cyclodextrin-ferrocene inclusion complex modified carbon paste electrode for amperometric determination of ascorbic acid

Inclusion complex of ferrocene (Fc) with beta-cyclodextrin (beta-CD) has been synthesized in ethylene glycol. It was unsolvable in water and had been successfully used to the preparation of beta-CD-Fc inclusion complex modified carbon paste electrode (CFCPE). Solid paraffin was used as the binder of the electrode. Ascorbic acid (AA) was electrocatalytically oxidized at the electrode in NH(3)-NH(4)Cl buffer (pH 10.0) with a anodic peak potential of +0.20 V (vs. SCE). The anodic current was proportional to the concentration of AA in the range 1.0x10(-3)-5.0x10(-7) mol l(-1) with the detection limit of 1.0x10(-7) mol l(-1). Using the inclusion complex as the electroactive substance greatly increased the stability and reproducibility of CFCPE than using Fc; the lifetime of the electrode can be over 1 year. Because CFCPE responds rapidly and sensitively, it has been successfully applied to the determination of AA in fruit juices.     

Fluorimetric and mass spectrometric study of the interaction of beta-cyclodextrin and osthole

The inclusion complex of beta-cyclodextrin (beta-CD) and osthole was studied by the electrospray ionization mass spectrometry (ESI-MS) and fluorescence spectrometry. From the mass spectrum, the 1:1 stoichiometric inclusion complex of beta-CD and osthole was observed. The tandem mass spectrum was performed. The fluorescence intensity of osthole increased in the present of beta-CD. According to the 1:1 beta-CD-osthole mode, the dissociation constant (KD) was obtained by ESI-MS and fluorescence spectrometry. The KD of beta-CD-osthole inclusion complex is 6.96 x 10(-3) mol L(-1) obtained by mass spectrometry and that is 8.14 x10 (-3) mol L(-1) obtained by fluorescence spectrometry, which is consistent with each other.     

Study of inclusion complex formation between tropaeolin OO and beta-cyclodextrin by spectrophotometry and Infrared spectroscopy

The mechanism of the inclusion of tropaeolin OO (TPOO) and beta-cyclodextrin (beta-CD) has been studied by spectrophotometry. The inclusion depth of the guest molecule in the host molecule was demonstrated by infrared spectrometry. Effect of the pH, concentrations of beta-CD, solvents and ionic strength on the inclusion of TPOO and beta-CD were examined. The result showed that TPOO reacts with beta-CD to form a 1:1 host-guest complex with an apparent formation constant of 1.50 x 10(3) l mol(-1). The thermodynamic parameters of inclusion reaction, DeltaG degrees , DeltaH degrees and DeltaS degrees were obtained.     

Spectrofluorimetric study of the beta-cyclodextrin:vitamin K3 complex and determination of vitamin K3

Vitamin K(3) (menadione) is an oil-soluble vitamin and not naturally fluorescent but yields fluorescence when it is reduced. However, it is possible to yield a fluorescent derivative in the region of 407 nm in aqueous medium when complexed to beta-cyclodextrin (CD). A 1:1 stoichiometric ratio and a formation constant of 373+/-34 l mol(-1) were obtained for the binary inclusion complex between menadione and beta-CD. The measurements were performed at pH 6.2 adjusted by adding 0.1 mol l(-1) citrate buffer solution and 6.4 x 10(-3) mol l(-1) of beta-CD concentration. The calibration graph was linear over the range 0.1-2.0 mg l(-1) with a repeatability of 2.2%; the detection limit was 0.022 mg l(-1) and the limit of quantification limit was 0.073 mg l(-1). The procedure was applied to pharmaceutical formulations.     

Determination of dissociation constants of cyclodextrin-ligand inclusion complexes by electrospray ionization mass spectrometry

The inclusion complexes of four ligands binding to cyclodextrins (CDs) were studied by electrospray ionization mass spectrometry (ESI-MS) and the dissociation constants of the complexes were obtained. The 1:1 stoichiometric inclusion complex was found in the system of CD and fenbufen or aspirin. The obtained KD values of the inclusion complexes of fenbufen binding to alpha-CD and to beta-CD are 4.38x10(-4) mol L(-1) and 2.12x10(-4) mol L(-1), respectively. The KD values of the inclusion complexes of alpha-CD-aspirin and beta-CD-aspirin are 3.33x10(-4) mol L(-1) and 1.83x10(-4) mol L(-1), respectively. A non-linear least squares regression method was applied to validate the results which were consistent with each other. For the system of tetracycline hydrochloride and CD, the 1:1 and 1:2 stoichiometric inclusion complexes were found in the mass spectra. The KD,1 and KD,2 values of the 1:1 and 1:2 stoichiometric inclusion complexes of alpha-CD and tetracycline hydrochloride are 4.47x10(-4) mol L(-1) and 6.51x10(-4) mol L(-1), respectively, and those of beta-CD and tetracycline hydrochloride are 2.26x10(-4) mol L(-1) and 8.57x10(-4) mol L(-1), respectively. For the system of norfloxacin and CD, besides the 1:1 and 1:2 inclusion complexes, the 1:3 stoichiometric inclusion complex was also found. The KD,1, KD,2 and KD,3 of alpha-CD and norfloxacin inclusion complexes are 4.61x10(-4) mol L(-1), 6.05x10(-4) mol L(-1) and 1.45x10(-3) mol L(-1), respectively. The three KD values of beta-CD and norfloxacin are 1.96x10(-4) mol L(-1), 4.93x10(-4) mol L(-1) and 1.15x10(-3) mol L(-1), respectively.     

Electrochemistry and voltammetry of procaine using a carbon nanotube film coated electrode

A new rapid, convenient and sensitive electrochemical method is described for the determination of procaine in pharmaceutical preparations, based on the unique properties of a multi-wall carbon nanotube (MWNT) thin film. The electrochemical behavior of procaine at the MWNT film-coated glassy carbon electrode (GCE) was investigated in detail, showing that the MWNT-coated GCE exhibits electrocatalytic activity to the oxidation of procaine because of the significant peak current enhancement and the lowering of oxidation overpotential. Furthermore, the mechanism for the oxidation of procaine at the MWNT-coated GCE was also studied. Finally, various experimental parameters such as solution pH value, the amount of MWNT, accumulation conditions and scan rate were optimized for the determination of procaine, and a new method with detection limit of 2 x 10(-7) mol/L was developed for procaine determination. This newly proposed method was successfully demonstrated with procaine hydrochloride injection.     

Spectrophotometric determination of procaine hydrochloride in pharmaceutical products using 1,2-naphthoquinone-4-sulfonic acid as the chromogenic reagent

Spectrophotometric determination of procaine hydrochloride is described. The procaine hydrochloride reacts with 1,2-naphthoquinone-4-sulfonic acid in pH 3.60 buffer solution to form a salmon pink compound, and its maximum absorption wavelength is at 484 nm, epsilon(484)=5.22 x 10(3).The absorbance for procaine hydrochloride from 0.30 to 100 microg ml(-1) obeys Beer's law. The linear regression equation of the calibration graph is C=19.23A-0.03, with a linear regression correlative coefficient is 0.9996, the detection limit is 0.28 microg ml(-1); recovery is from 98.0 to 105.2%. Effects of pH, surfactant, organic solvent, foreign ions, and standing time on the determination of procaine hydrochloride have been examined. This method is rapid and simple, and can be used for the determination of procaine hydrochloride in injection solution of procaine hydrochloride. The results obtained by this method agreed with those by the official method (dead-stop titration).     

Flow-injection chemiluminometric determination of some thioxanthene derivatives in pharmaceutical formulations and biological fluids using the [Ru(dipy)3(2+)]-Ce(IV) system.

A flow-injection (FI) methodology using tris(2,2'-dipyridyl)ruthenium(II), [Ru(dipy)3(2+)], chemiluminescence (CL) was developed for the rapid and sensitive determination of three thioxanthene derivatives, namely zuclopenthixol hydrochloride, flupentixol hydrochloride and thiothixene. The method is based on the CL reaction of the studied thioxanthenes with [Ru(dipy)3(2+)] and Ce(IV) in a sulfuric acid medium. Under the optimum conditions, calibration graphs were obtained over the concentration ranges 0.002-6 migrograms/ml for zuclopenthixol hydrochloride, 0.5-15 micrograms/ml for flupentixol hydrochloride and 0.05-7.5 micrograms/ml for thiothixene. The limits of detection (s/n = 3) were 4.2 x 10(-9) mol/l zuclopenthixol hydrochloride, 2 x 10(-8) mol/l flupentixol hydrochloride and 4.5 x 10(-8) mol/l thiothixene. The method was successfully applied to the determination of these compounds in dosage forms and biological fluids.     

Resonance scattering spectral analysis of chlorides based on the formation of (AgCl)n(Ag)s nanoparticle

A novel resonance scattering spectral method has been proposed for the determination of trace amounts of chlorides in the range of 2 x 10(-7)-8 x 10(-6) mol/l. It was based on the photochemical reaction system of AgNO3-NaCl-sodium oxalic to form the (AgCl)nucleus (n)(Ag)shell (s) nanoparticle. There is a strongest resonance scattering peak at 470 nm and a maximum absorption peak at 425 nm. The concentration of chlorides is proportional to the intensity of resonance scattering at 470 nm. The nonlinear resonance scattering peaks of the nanoparticle system have been also considered, according to the theory of the interaction between the surface electron of nanoparticle and the incidence photon.     

Investigation of the Belousov-Zhabotinsky reaction by thermal lensing

The supramolecular interaction of rubidate (chemically 2,3-naphthalenedicarboxylic acid, 1,4-dihydroxy-diethyl ester) and beta-cyclodextrin (beta-CD) has been studied by spectrofluorimetry. The influence of temperature on the supramolecular system has also been investigated and the thermodynamic parameters were calculated. The results show that beta-CD reacts with rubidate to form a 1:1 host-guest complex with an apparent association constant of 566+/-23 l mol(-1). It was also demonstrated that the thermodynamics of beta-CD-rubidate complex displayed a compensatory enthalpy-entropy relationship. Based on the significant enhancement of the fluorescence intensity of rubidate produced through complex formation, a spectrofluorimetric method for the determination of rubidate in bulk aqueous solution in the presence of beta-CD was developed. The linear relationship between the fluorescence intensity and rubidate concentration was obtained in the range from 2.7x10(-2) to 3.0 mug ml(-1), with a correlation coefficient of 0.9988. The detection limit was 8.2 ng ml(-1) and the relative standard deviation was 1.6%. There was no interference from the excipients normally used in tablet formulations. The application of the present method to the determination of rubidate in tablets gave satisfactory results and was compared with the reference method.     

Fluorometric study of the inclusion interaction of beta-cyclodextrin derivatives with tetraphenylporphyrin and its analytical application

The effects of native beta-cyclodextrin (beta-CD) and four kinds of alkylated beta-cyclodextrin (beta-CDs), i.e. heptakis (2,6-di-O-isobutyl-beta-cyclodextrin) (I), heptakis (2,6-di-O-octyl-beta-cyclodextrin) (II), heptakis (2,6-di-O-dodecyl-beta-cyclodextrin) (III), and heptakis (2,6-di-O-hexadecyl-beta-cyclodextrin) (IV), on the fluorescence behaviors of tetraphenylporphyrin (TPP) are investigated. An obvious fluorescence enhancement is observed from TPP by using alkylated derivatives compared to that obtained in beta-CD aqueous or in water. A 114-N fluorescence emission intensity enhancement is found for the complex with 2,6-di-O-octyl-beta-cyclodextrin relative to the free analyte. The exact stoichiometric ratios and the formation constants of the inclusion complexes have been examined by application of curve fitting method. The linear calibration plots between fluorescence intensity and TPP concentration are determined in the 1.14 x 10(-8)-5.06 x 10(-6) mol l(-1) range.     

Rayleigh light scattering study on the supramolecular interactions of beta-cyclodextrin derivatives with tetrakis(4-methoxylphenyl)porphyrin

The supramolecular interactions of beta-cyclodextrin(beta-CD) and four kinds of alkylated beta-cyclodextrin (beta-CDs), i.e. heptakis (2,6-di-O-isobutyl)-beta-cyclodextrin (Ob-beta-CD), heptakis (2,6-di-O-n-octyl)-beta-cyclodextrin (Oc-beta-CD), heptakis (2,6-di-O-n-dodecyl)-beta-cyclodextrin (Od-beta-CD) and heptakis (2,6-di-O-n-hexadecyl)-beta-cyclodextrin (Oh-beta-CD) with tetrakis(4-methoxylphenyl)porphyrin (TMOPP) have been investigated by Rayleigh light scattering (RLS) technique. Beta-CDs form 2:1 inclusion complex with TMOPP following an obvious RLS enhancement of TMOPP. The inclusion abilities of different beta-CDs were compared. The results show that the inclusion ability of beta-CDs is related to the size of the alkylated substituent. Thus, a new mechanism of inclusion interaction has been proposed. The exact stoichiometric ratios and the association constants of the inclusion complexes have been examined by application of curve fitting method.     

Flow injection spectrofluorimetric study of the supramolecular interaction between beta-cyclodextrin and dequalinium chloride and its analytical application

The supramolecular interaction of dequalinium chloride (DQC) and beta-cyclodextrin has been studied by flow injection spectrofluorimetry. The results showed that beta-CD reacted with DQC to form a 1:1 host:guest complex with an apparent association constant of 4.99 x 10(2) L mol(-1). Based on the enhancement of the fluorescence intensity of DQC, a flow injection spectrofluorometric method for the determination of DQC in bulk aqueous solution in the presence of beta-CD was developed. The linear range was 0.0412-30.00 microg mL(-1). The detection limit was 12.3 ng mL(-1) with a sampling rate of 80 h(-1). There was no interference from the excipients normally used in tablets and serum compositions. The proposed method was successfully applied to the determination of DQC in tablets and serum.