| Resonance Rayleigh scattering(RRS) and resonance non-linear scattering(RNLS) are new technologies developed in 1990s.Due to their remarkable characteristics of high sensitivity and simple operation,RRS and RNLS have received much attention. They have been extensively and successfully unitized to study and determination of such biological macromolecules as proteins,nucleic acids and polysaccharides,as well as pharmaceuticals,organic compounds and nanoparticles.In recent years,they have been more and more applied in environmental analysis,which show that RRS and RNLS have broad application potential in field of environmental analysis.This would become a new field for extending the application of these two techniques and a new way for developing environmental analysis.Therefore,taking anion surfactants, hydrogen chloride,chloride,metal ions such as aluminum(Ⅲ) and mercury(Ⅱ) as examples,we have studied and developed new systems and methods for the determination of the above analytes in environment using RRS and RNLS techniques.1 The Study on the Determination of Some Anionic Surfactants by Resonance Rayleigh Scattering and Resonance Non-Linear Scattering Spectra(1) Resonance Rayleigh Scattering and Resonance Nonlinear Scattering of the Interaction of Chlorpromazine Hydrochloride with Anionic Surfactants and Its Analytical ApplicationIn pH 3.0-5.0 acetate(HAc-NaAc) buffer media,chlorpromazine hydrochloride can react with some anionic surfactants such as sodium dodecylbenzene sulfonate, sodium dodecyl sulfate or sodium lauryl sulfonate.As a result,the spectra of absorption and fluorescence changed a little,but the resonance Rayleigh scattering(RRS) was enhanced greatly,and a new RRS spectrum appeared.At the same time,their resonance non-linear scattering(RNLS) such as second-order scattering(SOS) and frequency doubling scattering(FDS) were also increased.The maximum RRS wavelengths of three anionic surfactants were located at 277,369 and 278 nm.Their maximum scattering peaks were at 548 nm for SOS and 393 nm for FDS,respectively.The sensitivity of RRS method was much higher than those of SOS and FDS.The detection limits for three anionic surfactants were 0.018μg·mL-1 for sodium dodecylbenzene sulfonate,0.046μg·mL-1 for sodium dodecyl sulfate and 0.200μg·mL-1 for sodium lauryl sulfonate.There was a linear relationship between the RRS intensity and the drug concentration in the range of 0.06-10.0μg·mL-1 for sodium dodecylbenzene sulfonate, 0.15-15.0μg·mL-1 for sodium dodecyl sulfate and 0.67-12.5μg·mL-1 for sodium lauryl sulfonate,respectively.In this work,the spectral characteristics of the absorption, fluorescence,RRS,SOS and FDS,the optimum conditions of the reaction and the properties of analytical chemistry were investigated.A sensitive,simple and new method for the determination of anionic surfactants based on RRS has been developed.(2) Resonance Rayleigh Scattering Spectra of the Interaction of Co(Ⅱ)-2-(5-Bromo-2-Pyridylaro)-5-Diethylaminophenol with Sodium Dodecylbenzene Sulfonate and Its Analytical ApplicationIn pH 1.8-3.0 Britton-Robinson(BR) buffer medium,Co(Ⅱ) reacts with 5-Br-PADAP(2-(5-bromo-2-pyridylaro)-5-diethylaminophenol,HL) to form a cationic chelate Co[(HL)2]2+.In this case,only the characteristics of the absorption spectra changed,but the intensity of the resonance Rayleigh scattering(RRS) didn't increase. When the cationic chelate reacts further with some anionic surfactants such as sodium dodecylbenzene sulfonate(SDBS),sodium dodecyl sulfate(SDS) and sodium lauryl sulfonate(SLS),only SDBS can form a ternary ion-association complex and result in the enhancement of the resonance Rayleigh scattering(RRS) enhanced greatly.But, both of SDS and SLS do not have the similar reaction.The RRS peaks for the ion-association complex are located at 306,370 and 650 nm,respectively.There was a linear relationship between the RRS intensity(A/RRs) and the SDBS concentration in a certain range,the detection limits was 0.043μg·mL-1 and the linear range was 0.14-7.00μg·mL-1 at 650 nm.In this work,the characteristics of the RRS spectrum,the optimum conditions of the reaction and the properties of analytical chemistry were investigated.A new method for selective determination of SDBS in the presence of some other anionic surfactants such as SDS and SLS has been developed.The method is sensitive,simple and fast,which can be applied to the determination of SDBS in natural water and waste water samples with satisfactory results.In this work,the reaction mechanism was also discussed.(3) Resonance Rayleigh Scattering Spectra of the Interaction of Co(Ⅱ)-4-[(5-Chloro-2-pyridyl) azo]-1,3-diaminobenzene with Sodium Dodecylbenzene Sulfonate and Its Analytical ApplicationIn pH 1.8-3.0 Britton-Robinson(BR) buffer solution,cobalt(Ⅱ) reacts with 4-[(5-Chloro-2-pyridyl) azo]-1,3-diaminobenzene(5-Cl-PADAB,L) to form a cationic chelate[COL2]2+.When interacting with anionic surfactants such as sodium dodecyl benzene sulfonate(SDBS),sodium dodecyl sulfate(SDS) or sodium dodecyl sulfonate (SLS),the chelate can only react with SDBS to form ternary ion-association complexes ([CoL2][SDBS]2).By virtue of the extrusion action of water and Van der Waals force, the hydrophobic ion-association complexes draw close to each other and further aggregate to form {[CoL2][SDBS]2}n nanoparticles with an average diameter of 30 nm. As a result,resonance Rayleigh scattering(RRS) is enhanced greatly and new RRS spectra appear.Under the same conditions,both SDS and SLS exhibit no similar reactions and do not result in obvious change of RRS.Therefore,SDBS can be determined selectively by RRS method in the presence of SDS or SLS.When 516 nm was chosen as a detection wavelength,the linear range and the detection limit(3σ) are 0.05-6.00μg mL-1 and 0.015μg mL-1 for the determination of SDBS,respectively.The characteristics of RRS spectra of the[CoL2]2+-SDBS system,the optimum conditions of the reaction and the influencing factors have been investigated.The effects of coexisting substances were examined too,which indicated a good selectivity of the method for the determination of SDBS.The method can be used for the determination of SDBS in waste water and fiver water samples,and the results are satisfactory compared with those of standard samples of SDBS.Based on the formation of {[CoL2][SDBS]2}n nanoparticles,a sensitive,simple and rapid method has been developed for the determination of SDBS in environmental water samples using a RRS technique. Moreover,the reaction mechanism was discussed.2 The Study on the Determination of Hydrochloride and Chloride by Resonance Rayleigh Scattering and Resonance Non-Linear Scattering Spectra(1) Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Ag+-Cl--Fluorescein Dye System and Their Analytical ApplicationIn pH 3.5-4.4 acetate(HAc-NaAc) buffer solution,AgCl formed by the reaction of Ag+ with Cl- can bind with excessive Ag+ to form a[AgCl·Ag]+ cation.The cation further reacts with fluorescein anion(HL) to form ion-association complexes [(AgCl·Ag)HL]by virtue of electrostatic attraction and hydrophobic force.Then the complexes draw close to each other and further aggregate to produce[(AgCl·Ag)HL]n nanoparticles with an average diameter of 20 nm due to the extrusion action of water and Van der Waals force.As a result,the spectra of absorption and fluorescence were changed a little,but resonance Rayleigh scattering(RRS) and resonance non-linear scattering(RNLS) such as frequency doubling scattering(FDS) and second-order scattering(SOS) were enhanced greatly.The maximum wavelengths of RRS,FDS and SOS were located at 313,349 and 564 nm,respectively.The increments of three scattering intensity(△IRRS,△IFDS and△ISOS) were directly proportional to the concentration of Cl- in certain ranges,and three scattering methods could be applied to the determination of Cl-.The sensitivity of RRS method was the highest among the three scattering methods.The linear range and the detection limit for Cl- using RRS method were 0.006-1.90μg·mL-1 and 1.9 ng·mL-1.In analysis of hydrochloride(HC1) in environmental air or inorganization discharge of waste gas samples,the linear range and the detection limit were 0.001-0.33 mg·m-3 and 3.30×10-4 mg·m-3 when the sampling volume of air was 60 L;In organization discharge of waste gas samples,the linear range and the detection limit were 0.008-2.00 mg·m-3 and 2.00×10-3 mg·m-3 for HCl when the sampling volume of air was 10 L.In this work,the influences of[(AgCl·Ag)HL]n nanoparticles on the spectra of absorption,fluorescence,RRS and RNLS,the optimum conditions and the influencing factors have been investigated.Meanwhile,the effects of coexisting substances have been discussed and the results show that the method has good selectivity.Based on the above researches,a highly sensitive,selective,simple and fast method for the determination of HC1 in environmental air and waste gas samples and chloride in environmental water samples by RRS,SOS and FDS techniques has been developed.In addition,the reaction mechanism was discussed.(2) Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Ag+-Cl--Dihalogenated Fluorescein Dyes Systems and Their Analytical ApplicationIn pH 3.2-6.2 acetate(HAc-NaAc) buffer solution,AgCl formed by the reaction of Ag+ with Cl- can bind with excessive Ag+ to form a[AgCl·Ag]+ cation.The cation further reacts with dihalogenated fluorescein dyes(dichlorofluorescein, dibromofluorescein,diiodofluorescein) anion(HL-) to form ion-association complexes [(AgCl·Ag)HL]by virtue of electrostatic attraction and hydrophobic force.Then the hydrophobic complexes draw close to each other and further aggregate to form [(AgCl·Ag)HL]n nanoparticles with an average diameter of 20 nm due to the extrusion action of water and Van der Waals force.As a result,the spectra of absorption and fluorescence were changed a little,but resonance Rayleigh scattering(RRS) and resonance non-linear scattering(RNLS) such as frequency doubling scattering(FDS) and second-order scattering(SOS) were enhanced greatly.The sensitivity of Ag+ -Cl--dichlorofluorescein system was the highest among three systems.Its maximum wavelengths of RRS,FDS and SOS were located at 314,349 and 564nm,respectively. The increments of three scattering intensity(△IRRS,△IFDS and△ISOS) were directly proportional to the concentration of Cl- in certain ranges,and three scattering methods could be applied to the determination of Cl-.Among them,the RRS method has the highest sensitivity,and followed by the FDS method.The linear ranges and the detection limits for Cl- of the three methods(RRS,FDS and SOS) were 0.006-1.94μg·mL-1,0.030-2.20μg·mL-1,0.074-1.94μg·mL-1 and 1.7 ng·mL-1,8.9 ng·mL-1,22.1 ng·mL-1,respectively.In analysis of hydrogen chloride(HC1) in environmental air or inorganization discharge of waste gas samples,the linear ranges and the detection limits were 0.001-0.333 mg·m-3,0.005-0.375 mg·m-3,0.012-0.333 mg·m-3 and 3.0×10-4 mg·m-3, 1.5×10-3 mg·m-3,3.8×10-3 mg·m-3 when the sampling volume of air was 60 L;In organization discharge of waste gas samples,the linear ranges and the detection limits were 0.006-2.00 mg·m-3,0.031-2.25 mg·m-3,0.074-2.00 mg·m-3 and 1.8×10-3 mg·m-3, 9.2×10-3 mg·m-3,2.2×10-2 mg·m-3 for HCl when the sampling volume of air was 10 L.In this paper,the influences of[(AgCl·Ag)HL]n nanoparticles on the spectra of absorption, fluorescence,RRS and RNLS,the optimum conditions and the influencing factors have been investigated.Meanwhile,the effects of coexisting substances have been discussed and the results show that the method has good selectivity.Based on the above researches,a highly sensitive,selective,simple and fast method for the determination of HCl in environmental air and waste gas samples and chloride in environmental water samples by RRS,SOS and FDS techniques has been developed.In addition,the reaction mechanism was discussed.(3) Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Ag+-Cl--Polysubstituted Fluorescein Dyes Systems and Their Analytical ApplicationIn pH 3.2-5.7 acetate(HAc-NaAc) buffer solution,AgCl formed by the reaction of Ag+ with Cl- can bind with excessive Ag+ to form a[AgCl·Ag]+ cation.The cation further reacts with Polysubstituted fluorescein dyes(eosin B,eosin Y,tiger red,phloxine and ethyl eosin) anion(HL-) to form ion-association complexes[(AgCl·Ag)HL]by virtue of electrostatic attraction and hydrophobic force.Then the complexes draw close to each other and further aggregate to produce[(AgCl·Ag)HL]n nanoparticles with an average diameter of 20 nm due to the extrusion action of water and Van der Waals force. As a result,the spectra of absorption and fluorescence were changed a little,but resonance Rayleigh scattering(RRS) and resonance non-linear scattering(RNLS) such as frequency doubling scattering(FDS) and second-order scattering(SOS) were enhanced greatly.The sensitivity of Ag+-Cl--eosin B system was the highest among six systems.Its maximum wavelengths ofRRS,FDS and SOS were located at 315,349 and 564 nm,respectively.The increments of three scattering intensity(△IRRS,△IFDS and△ISOS) were directly proportional to the concentration of Cl- in certain ranges,and three scattering methods could be applied to the determination of Cl-.Among them,the FDS method has the highest sensitivity,and followed by the RRS method.The linear ranges and the detection limits for Cl- of the three methods(RRS,FDS and SOS) were 0.005-1.22μg·mL-1,0.004-2.92μg·mL-1,0.01-1.94μg·mL-1 and 1.5 ng·mL-1,1.2ng·mL-1, 3.9 ng·mL-1,respectively.In analysis of hydrochloride(HCl) in environmental air or inorganization discharge of waste gas samples,the linear ranges and the detection limits were 0.0008-0.21mg·m-3,0.0007-0.50 mg·m-3,0.002-0.33 mg·m-3 and 2.50×10-4 mg·m-3, 2.00×10-4 mg·m-3,6.70×10-4 mg·m-3 when the sampling volume of air was 60 L;In organization discharge of waste gas samples,the linear ranges and the detection limits were 0.005-1.25 mg·m-3,0.004-3.00 mg·m-3,0.01-2.00 mg·m-3 and 1.50×10-3 mg·m-3, 1.20×10-3 mg·m-3,4.00×10-3 mg·m-3 for HCl when the sampling volume of air was 10 L. In this paper,the influences of[(AgCl·Ag)HL]n nanoparticles on the spectra of absorption,fluorescence,RRS and RNLS,the optimum conditions and the influencing factors have been investigated.Meanwhile,the effects of coexisting substances have been discussed and the results show that the method has good selectivity.Based on the above researches,a highly sensitive,selective,simple and fast method for the determination of HC1 in environmental air and waste gas samples and chloride in environmental water samples by RRS,SOS and FDS techniques has been developed.In addition,the reaction mechanism was discussed.3 Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Aluminum(Ⅲ)-Chromazol KS-Cetyipyridinium Bromide System and Their Analytical ApplicationIn the pH 5.8-6.5 acetate(HAc-NaAc) buffer medium,Al(Ⅲ) can react with chromazol KS to form an chelated anion which can further react with cetylpyridinium bromide(CPB) to form hydrophobic ion-association complexes Al(OH)[H2L(CP)4]2. Then the complexes can draw close to each other and further aggregate to form {Al(OH)[H2L(CP)4]}n nanoparticles with an average diameter of 50 nm due to the extrusion action of water and Van der Waals force.As a result,resonance Rayleigh scattering(RRS) and resonance non-linear scattering(RNLS) such as second-order scattering(SOS) and frequency doubling scattering(FDS) were enhanced greatly.Its maximum wavelengths of RRS,SOS and FDS were located at 277,550 and 350 nm, respectively.The increments of three scattering intensity(△IRRS,△ISOS and△IFDS) were directly proportional to the concentration of Al(Ⅲ) in certain ranges,and three scattering methods could be applied to the determination of Al(Ⅲ).The linear ranges and the detection limits for Al(Ⅲ)by the three methods(RRS,SOS and FDS) were 0.76-30.0 ng·mL-1,0.73-35.0 ng·mL-1,1.03-35.0 ng·mL-1 and 0.23 ng·mL-1,0.22 ng·mL-1,0.31 ng·mL-1,respectively.In the paper,the spectral characteristics of the RRS, SOS and FDS,the optimum conditions and the influencing factors have been investigated.These shows the method have a good selectivity.Based on the reaction,we develop a new method which is sensitive,simple and rapid to determinate Al(Ⅲ).The method can be applied to the determination of Al(Ⅲ) in the real water samples,and the result is satisfactory.In addition,the reaction mechanism was discussed.4 Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Mercury(Ⅱ)-Iodide-Tetradecyl Pyridinium Bromide System and Their Analytical ApplicationIn pH 1.8-6.0 Britton-Robinson(BR) buffer medium,Hg(Ⅱ) can react with I- to form a complex anion([HgI4]2-),which can only lead to the small changes of resonance Rayleigh scattering(RRS) and resonance non-linear scattering(RNLS).The complex anion can further react with tetradecyl pyridinium bromide(TPB) to form hydrophobic ion-association complex.Then the complexes can draw close to each other and further aggregate to form nanoparticles with an average diameter of 10 nm due to the extrusion action of water and Van der Waals force.As a result,resonance Rayleigh scattering (RRS) and resonance non-linear scattering(RNLS) such as frequency doubling scattering(FDS) and second-order scattering(SOS) were enhanced greatly.The maximum RRS,FDS and SOS wavelengths of the ion-association complex were located at 366,390 and 570 nm,respectively.The increments of three scattering intensity(△IRRS,△IFDS and△ISOS) were directly proportional to the concentration of Hg(Ⅱ) in certain ranges,and three scattering methods could be applied to the determination of Hg(Ⅱ).The linear ranges and the detection limits for Hg(Ⅱ) were 0.003-0.125μg·mL-1 and 0.8 ng·mL-1(RRS),0.003-0.100μg·mL-1 and 0.9 ng·mL-1 (FDS),and 0.004-0.100μg.mL-1 and 1.2 ng·mL-1(SOS),separately.The sensitivity of RRS method was higher than those of SOS and FDS methods.In the paper,the RRS and RNLS spectral characteristics of ion-association complexes,the optimum conditions and the quality of analytical chemistry,the influencing factors have been investigated.In addition,the reaction mechanism and the size of ion-association complexes were discussed.Based on the ion-association reaction,we developed new methods which are sensitive,simple and rapid to determinate Hg(Ⅱ).The methods can be applied to the determination of Hg(Ⅱ) in the surface water,sewage and wet precipitation samples with satisfactory results.
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