| When the material molecule receives electromagnetic radiation or light,the energy transitions will take place via rotation,vibration or electronic transitions.So,the reflection,absorption,emission or scattering will occur,molecular spectrometry is the relative intensity of electromagnetic radiation of each frequency,including ultraviolet-visible(UV-vis) spectroscopic analysis,infrared(IR) spectroscopic analysis, Raman spectroscopic analysis,fluorescence(FL) spectroscopic analysis,resonance Rayleigh scattering(RRS) and so on.Their characteristics are simple,rapid and highly sensitive.Especially,RRS has attracted more and more attention due to its high sensitivity and simplicity.It has been extensively and successfully unitized to study and determination of biological macromolecules,trace metal ions,nonmetal ions and nanoparticle probe et al.However,molecular spectroscopic techniques have a certain limitation of simultaneous determination of multicomponent and complicated samples. Commonly,each composition in the complicated samples is mensurated respectively before the samples are separated by tedious process.Recently,the simultaneous determination of multicomponent mixture that is not separated has attracted more and more attention.At present,the simultaneous determination is accomplished by molecular spectroscopic analysis methods mainly combined with derivative technique, polarization technique,time-resolved fluorescencee and chemometrics.Phenothiazine compounds are widely used to inhibit central nervous system,antipsychotic medication, antihistamines and dyes.This paper tells the determination of each composition in the mixed system consists of above substance by two lines with one same point-RRS spectra,partial least square(PLS)-micellar enhanced fluorescence and derivative-synchronous fluorescence,and several new methods have been developed for the simultaneous determination of multicomponent phenothiazine compounds.The main results and conclusions are summarized as follows:1.Study on the interaction between phenothiazine drugs and isopolyacids and their simultaneous determination by resonance Rayleigh scattering spectra combined with measurement analtsis of two lines with one pointUnder the optimum acidity,three isopolyacids,including ammonium molybdate (AM),sodium tungstate(ST) and ammonium metavanadate(AV),can react with chlorpromazine hydrochloride(CPH) and promethazine hydrochloride(PMH) to form ion-association complexes,which can result in the great enhancement of resonance Rayleigh scattering(RRS) and the appearance of new RRS spectra.And there was an obvious difference of RRS spectra of three isopolyacids systems and their increments of RRS intensity were followed by this sequence,AM(pH 1.1)＞AV(pH 5.20)＞ST(pH 4.0).So,AM,the most sensitive RRS probe,was taken as an example to the further studies on the interaction with CPH and PMH.The reaction products of AM-CPH and AM-PMH have similar spectral characteristics as the maximum RRS peaks ara all at 365 nm and the increments of scattering intensity(ΔIRRS) are directly proportional to the concentrations of drugs in certain ranges.However,their linear amplifications are a great difference as their concentration.Based on the differences and the additivity of RRS intensity,a novel method for simultaneous determination of CPH and PMH had been developed with "measurement analysis of two lines with one same point".The detection limits(3σ) for CPH and PMH are 4.5 ng·mL-1,7.7 ng·mL-1,respectively,and all the linear ranges are 0.03～2.4μg·mL-1.In this work,the RRS spectral characteristics and the optimum conditions of the reactions were investigated as well as the properties of the analytical chemistry.The mechanism of ion-association reaction and the reasons for the enhancement of scattering spectra were discussed by the quantum chemistry method.In addition,the influence of coexistence were tested,the result showed that the method has a good selectivity.The method had been applied to simultaneous determination of CPH and PMH in serum and urine samples and phenergan cough syrup with satisfactory result.2.Study on the interaction between phenothiazine drugs and anion surfactants and their simultaneous determination by resonance Rayleigh scattering spectra combined with measurement analtsis of two lines with one pointUnder the optimum acidity,three anion surfactants as sodium dodecyl sulfate (SDS),sodium dodecyl sulfonate(SLS) and sodium dodecyl benzene sulfonate(SDBS) can all react with chlorpromazine hydrochloride(CPH) and promethazine hydrochloride (PMH) to form ion-association complexes.As,a result,the resonance Rayleigh scattering(RRS) is enhanced greatly and the new RRS spectra appear.The studied six systems have similar spectral characteristics which the maximum RRS peaks are all located at 276 nm,and there are the small peaks at 360 nm.And the scattering intensities(ΔIRRS) are enhanced with the increase of medication concentration in certain ranges.After CPH and PMH were mixed at a ratio of 1:1,a series of the different concentrations of the mixture drugs reacted with anion surfactants.The RRS intensities are also directly proportional to the total concentrations of CPH and PMH at 276 nm. The results showed that the RRS intensities of CPH and PMH have the additivity. Hence,the calibration curve for the mixture system was constructed,and the total concentration of CPH and PMH in mixed samples was obtained.Furthermore,there was an obvious difference of RRS spectra of the bound products for CPH and PMH,and their increments of RRS intensity were followed by this sequence,CPH＞PMH.So, measurement analysis of two lines with one same point can be constructed for the simultaneous determination of both component systems.Due to the remarkable difference of sensitivity of the different anion surfactants for the same phenothiazine drugs,which are followed by this sequence,SDBS＞SDS＞SLS,SDBS are taken as an example to the further studies on the simultaneous determination of CPH and PMH by RRS spectra combined with measurement analysis of two lines with one same point. Takeing SBDS as RRS probe,the detection limits and the linear ranges are 8.3 ng·mL-1, 0.03～3.6μg·mL-1 for CPH and 11.5 ng·mL-1,0.06～3.2μg·mL-1 for PMH.The optimum conditions of reaction and the effects of foreign substances have been investigated.Based on the reaction between phenothiazine drugs and anion surfactants, a new method of simultaneous determination for CPH and PMH has been developed by RRS spectra combined with measurement analysis of two lines with one same point. The method is simple,rapid and sensitive,can be applied to determinate CPH and PMH in pharmaceuticals and urine samples and phenergan cough syrup.3.Simultaneous determination of ehlorpromazine hydrochloride,promethazine hydrochloride and trifluoperazine hydrochloride by partial least sqnare-micellar enhanceed fluorescence spectrometryIt was found that in Tris-HCl buffer solution of pH 7.0,the addition of sodium dodecyl sulfate(SDS) to the solution of phenothiazine drugs,such as chlorpromazine hydroehloride(CPH),promethazine hydrochloride(PMH) and trifluoperazine hydrochloride(TFPH),showed a remarkable enhancement of their fuorescence intensities.A further study proved that the phenothiazine drugs can be determined by fluorophotometric method in micellar system.However,the overlapping of the fluorescence spectra of three phenothiazine drugs are serious,which will interfere in the simultaneous determination of them.So,diverse chemometris,including partial least square(PLS),principal component regression(PCR) classical least square(CLS),were introduced to resolve overlapped spectra and those methods were compared in terms of its resolution ability.The result showed that showed,among the three components system,it was the best for PLS to resolve overlapped spectra and forecast respective concentration of components,its RPET is 3.6%.Hence,a new method for simultanous determination of three phenothiazine drugs has been developed.The linear ranges of the calibration curves for three phenothiazine drugs are 0.0～3.80μg·mL-1(CPH),0.0～4.80μg·mL-1(PMH) and 0.0～4.00μg·mL-1(TFPH),respectively;the detection limits are 10.40 ng·mL-1 for CPH,9.53 ng·mL-1 for PMH and 6.18 ng·mL-1 for TFPH;the correlation coefficients are between 0.9969～0.9990.The methods are good selective and high sensitivity,so they can be applied to simultaneously determinate CPH,PMH and TFPH in the synthetic samples,and the RSD of calibration set are 3.73%(CPH), 4.0%(PMH) and 2.80%(TFPH),respectivelty;the RSD of prediction setare 2.10%for CPH,4.20%for PMH and 3.30%for TFPH.The analytical results of simultaneous determination of CPH,PMH and TFPH in pharmaceuticals and urine samples are satisfactory.4.Solvent extraction & derivative-synchronous fluorescence spectrometry on simultaneous determination of methylene blue and azure A in ion-association complex form with AuCl4-A synchronous fluorescence spectrometry combined with first order derivative has been developed for the simultaneous determination of methylene blue(MB) and azure A (AA).The method is based upon the formation of ion-association complexes of AuCl4-with MB and AA and solvent extraction of the two complexes by 1,2-dichloroethane in aciditive medium.When[MB][AuCl4]3 and[AA][AuCl4]2 complexes were synchronously scanned atΔλ=20 nm with first order derivative techniques treatmented in organic phase,the derivative-synchronous fluorescence peaks appeared at 683 nm for [MB][AuCl4]3 and 608 nm for[AA][AuCl4]2,respectively.The fluorescence intensities were directly proportional to the concentrations of MB at 683 nm and AA at 608 nm within certain range.So,a simple,sensitive method has been developed for the simultaneous determination of MB and AA.The detection limit(3σ) and linear range were 7.90 ng·mL-1 and 0.03～4.80μg·mL-1 for MB,17.8 ng·mL-1 and 0.06～5.80μg·mL-1 for AA.In this work,the spectral characteristics and composing of ion-association complexes,the optimum conditions and the influences on reaction system were investigated.The method can be applied to the simultaneous determination of AA and MB in urine samples and in AzureⅡwith satisfactory results.
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