| The gold nanoparticle is a kind of important nanoparticle material, which shows the potential applied value because of its especial physical and chemical characteries, has inspired people's great interest to study it. It has acted a very vital role in the analytical application study of nanoparticle. In recent ten years, resonance Rayleigh scattering (RRS) technique has attracted more and more attentions because of its high sensitivity, simplicity and good selectivity. It has been used for studying and detecting of biological macromolecules, basic dyes, cationic surfactants and some drugs with unmodified gold nanoparticle probes. With the development and further study , One found that the sensitivity of molecular spectrum detecting drugs with gold nanoparticle probe is many times or ten times higher than those of other reagents, this made determination of some trace drugs become possible, and exploited the more space to study gold nanoparticle in molecular spectrum area. Supported by the National Natural Science Foundation of China, this article investigates the process, mechanism and analytical application between the gold nanoparticle and some drugs small molecular compounds at the molecular level with resonance rayleigh scattering spectrum, resonance non-linear scattering spectrum, and combining the transmission electron microscope, uv-vis absorption and fluorescence method. Based on some Simple, rapid and highly sensitive molecular spectrum new methods for the determination of anthracycline anticancer drug such as epirubicin et al, bleomycins anticancer antibiotics, berberine and drug methylene blue with gold nanoparticle probe. Main investigated system are listed as follow:1. Resonance rayleigh scattering method for the determination of some anthracycline anticancer drugs with gold nanoparticle probeIn a neutral or weak alkaline medium, the gold nanoparticle can combine with an anthracycline anticancer drug such as epirubicin, daunorubicin or mitoxantrone by the virtue of electrostatic and hydrophobic interaction, forming aggregate with bigger diameters. As a result, the resonance Rayleigh scattering (RRS) was enhanced greatly, and a new RRS spectrum appeared. The maximum RRS signals of three ion-association complexes were all located at about 313 run, and there were another wide scattering strip between 510～610 run. There was a linear relationship between the RRS intensity and the drug concentration in the range of 0.009～0.5 for epirubicin, 0.010～0.7 for daunorubicin and 0.030～1.2μg·mL-1 for mitoxantrone, respectively. Their detection limits (3a) for three drugs were 2.7 for epirubicin, 3.1 for daunorubicin and 9.0 ng·mL-1 for mitoxantrone. In this work, the characteristics of the absorption, fluorescence and RRS spectra, the optimum conditions of the reaction and the properties of analytical chemistry were investigated. A sensitive, simple and new method for the determination of anthracycline anticancer drugs based on RRS has been developed.2. Effects of interaction of gold nanoparticle with some anthracycline anticancer drugs on second-order scattering and frequency doubling scattering and their analytical applicationThe second-order scattering(SOS) and frequency doubling scattering(FDS) spectra for the interaction of gold nanoparticle and an anthracycline anticancer drug such as epirubicin, daunorubicin or mitoxantrone are sdutied. The spectra characteristics, the effect factors, the optimum conditions of the reaction and the influence of foreign substances have been investigated. The sensitivity of SOS method was higher than those of FDS. The detection limits for three anthracycline anticancer drugs were 3.3 for epirubicin, 3.8 for daunorubicin and 5.2 ng·mL-1 for mitoxantrone. There was a linear relationship between the SOS intensity and the drug concentration in the range of 0.011～0.5 for epirubicin, 0.013～0.5 for daunorubicin and 0.017～0.8μg·mL-1 for mitoxantrone, respectively. A sensitive, simple and new method for the determination of anthracycline anticancer drugs based on SOS has been developed.3. highly sensitive resonance rayleigh scattering method for the determination of bleomycinA$ and bleomycinA2 with gold nanoparticleIn a pH 2.5～7.0 medium, the gold nanoparticle can combine with an anticancer drug such as bleomycinA2 (BLMA2) and bleomycinA5 (BLMA5), forming aggregate with bigger diameters. As a result, the resonance Rayleigh scattering (RRS) was enhanced greatly, and a new RRS spectrum appeared. There was a linear relationship between the RRS intensity and the drug concentration in the range of 0.008-0.64 for BLMA2 and 0.016-0.24 for BLMA5, respectively. Their detection limits ( 3σ) for the two drugs were 1.6 for BLMA2 and 1.7 ng·mL-1 for BLMA5. It is applied to determine the BLMA5 and BLMA2 in serum and urine samples. The recovery range from 97.3 % to 102%. In this work, the spectral characteristics of the RRS, the optimum conditions of the reaction and the properties of analytical chemistry are investigated. The formation of aggregates and the reasons of enhanced resonance scattering are discussed.4. highly sensitive spectrophotometric method for the determination of berberine with gold nanoparticleIn pH 3.0～4.7 NaC6H7O7-HCl buffer solution, the gold nanoparticle reacts with berberine hydrochloride to form a binding product. As the result, the color of solution changed to blue from red, and the absorption spectra was changed a lot. The maximum absorption wavelength red shift to 660 nm from 518 nm (Δλ=142 nm). This reaction has highly sensitivity,εmax=1.86×105 L·mol-1·cm(-1), which is obeyed Beer law among the concentration of bererine in 2.0×10-8～3.22×10-6mol·L-1. And this method has also good selectivity, so a highly sensitive, simple new spectrophotometric method for the determination of berberine with gold nanoparticle has been developed.The method can be applied to determination of berberine in some medicaments. 5. resonance rayleigh scattering spectral method for the determination of methylene blue with gold nanoparticle as brobeIn a citrate contained solution, anion of citrate self-assembled on Au nanoparticle's surface with positive charge, making Au nanoparticle become a super-moleculor compound with negative charge surrounded by citrate. In a neutral or weak alkaline medium pH 6.5～9.5, the super-moleculor compound can combine with methylene blue by the virtue of electrostatic and hydrophobic interaction, forming aggregate with bigger diameters (average diameter increase from 12 nm to 20 nm ). The aggregate arouse plasmon absorption band of gold nanoparticle evident bathochromic effect (Δλ=144 nm) , Resonance Rayleigh Scattering (RRS) intensity can be enhanced greatly and the resonance nonlinear scattering such as Frequency Double Scattering (FDS) and Second Order Scattering (SOS) can be enhanced markedly as well. The maximum scattering peaks are at 371 nm for RRS, 280 nm for FDS and 540 nm for SOS respectively. In optimum conditions, there is a linear relationship between scattering intensity (ΔI) and the concentration of methylene blue, and the highest sensitivity is RRS. So gold nanoparticle can be the RRS probe of high sensitivity for methylene blue, the detection limits of methylene blue is 21.17 ng·mL-1. The method has good selectivity and has been successfully applied to the detection of methylene blue in clinic serum samples. In addition, the reaction mechanism and the reasons for the enhancement of RRS are discussed. |
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