| According to the’12 Rules of Green Chemistry’, the new requirements of modern analytical chemistry are greenization of sample pretreatment and analytical technique. To be more precise, it requests miniaturization, real time and high-speed. With the increasing of analytical throughput and decreasing of sampling volumn, micro-and nano-volumn is being employed in analytical system, which asks new techniques to solve the problems of operation and detection appeared in micro and nano-scale. Micro scale analysis is the new advanced field focusing on solving operation of liquid and analysis of components. Lab on a chip, analysis in micro- and nano-scale, nano-particle biosensor etc. are the representatives of green analytical chemistry technique.The physical characteristics in micro and nano scale are different from in macro scale. For instance, size effect, fluid behavior are becoming the major factors of effecting separation and analysis in micro and nano scale. In this paper, usint TCMs as target, systematical analysis was performed including extract chip for sample pretreatment, separation and analysis by nanoLC-MS and ambient mass quick analysis. In addition, surface modification in micro scale and optimization of laminar flow in extract chip, solid phase extraction of carotenoids are also investigated in detail. All techniques employed in this paper fit the request of green analytical chemistry, miniaturization, real time and high-speed, very well. The main contents of these six chapters are as follows:1. Based on fluid behavior in micro-scale, using glass slides as model, superhydrophobic and superhydrophilic surface were established. Firstly,30-nm SiO2 nanoparticle was perpared by sol-gel method, then coating 30-nm SiO2 particle film on the surface was followed by etching via buffer oxide etch (BOE) to form a stable nano rough surface on the substrate of the surface. After this, the glass surface is superhydrophilic. The last, after silanization a superhydrophobic surface was formed (contact angle, CA:149.2°, on glass slide). Compared to the reported plasma method, this method more fits for modification of surface in micro channel.2. Modification and characterization of inner surface in micro fluidic chip. Based on the strategy of chapter one, using quartz capillary as model of micro fluidic channel, the modification and characterization were performed. The results prove that the strategy of dip-coating-etching method can be used to establish superhydrophobic and superhydrophilic surface on the inner surface of micro channel. Characterization in micro channel is always a difficult problem, which is different from the slide surface. In this part, the property of hydrophobic and hydrophilic surface in channel was characterized by capillary rise, and compared with the results of contact angle, the relativity is good (related coefficient is 0.9652), which affords a new and simple way for characterization of hydrophilic or hydrophobic property in micro channel. In addition, the gradient hydrophobic modification in micro channel was also performed, which may be used for modification of self-driven chip.3. A three-phase microfluidic chip was developed for rapid and efficient sample pretreatment of alkaloids in micro scale. Recently, three organic solvents having different viscosities and being greener than chloroform (ethyl acetate, n-butyl acetate, and hexyl acetate) were investigated as alternatives. When the viscosity of the solvent used as transport phase is close to that of water and it has favorable partition coefficients for alkaloids, for example n-butyl acetate, a high extraction efficiency can be achieved. When using n-butyl acetate as transport phase, over 90% of the alkaloids could be extracted into the acceptor phase in 25 sec and alkaloids in Cephaelis ipecacuanha, Strychnods seed, Atropa belladonna, Vinca minor and Coptidis rhizome can be successfully extracted.4. Compared with traditional HPLC, Micro/nano-HPLC is greener and low comsumption. However, the price of commercial nano-HPLC is really high. In this chapter, a homemade nano-LC based on traditional UPLC system was established, which is also successfully hyphenated with ESI-MS. Analysis of alkaloids in traditional Chinese medicine was performed by this homemade system. Compared with traditional HPLC, the tailing problem of alkaloids become less serious. When hyphenated with mass detector, the sensitivity of nano-LC-ESI-MS increased three orders of magnitude, and the solvent and sample consumption decreased dramatically. For an instance, if the time for analysis of one sample is 60 min, then 10 mL mobile phase can be used around 35 days and for 833 samples, which highlights the advantages of nanoLC-MS such as environment-friendly and low solvent and labor consumption.5. Since 2004, the development of ambient mass spectrometry, a lot of researchers devote themselves into this new hot field. The vital characters of ambient mass spectrometry is analysis of sample with a little or without sample pretreatment steps. In this chapter, high-speed analysis of Scutellaria bacalensis Georgi by Direct Analysis in Real Time (DART)-HRMS was performed. The information of aglycones and glycosides are got in seconds. In addition, a rapid, simple and unambiguous method for distinguishing between the morphologically similar Chinese star anise and toxic Japanese star anise is established. Adulteration down to 1%(w/w) is measurable. Compared with existing PCR, TLC, GC-MS and HPLC-ESI-MS/MS procedures, the proposed DART-HRMS procedure is faster and simpler, which is important for food safety issues.6. Carotenoids are organic pigments that are naturally occurring in the chloroplasts and chromoplasts of plants and some other photosynthetic organisms like algae, some types of fungus and some bacteria. There are over 600 known carotenoids; they belong to the category of tetraterpenoids (i.e. they contain 40 carbon atoms). Structurally they are in the form of a polyene chain which is sometimes terminated by rings, and are split into two classes, xanthophylls (which contain oxygen) and carotenes (which are purely hydrocarbons, and contain no oxygen). Carotenoids have many physiological functions. Nevertheless, carotenoids are unstable to light, heat, and oxygen. How to accurately determine the contents of the compounds in the body fluids has been a challenge to analysts. In this chapter, an on-line analytical system for the elution profile monitoring of solid-phase-extraction (SPE) cartridge was constructed. Using lutein and β-carotene as model moleculars, adsorption and desorption performances of carotenoids on the C18ã€C30ã€and silica SPE cartridges were investigated by the frontal analysis on the on-line analytical system. The optimal adsorption and desorption conditions have been proposed. The problems of decomposition and oxidation of carotenoids during the pretreatment of serum have been solved effectively by the proposed SPE method. After that, the SPE-C30 column HPLC method has been developed for the serum and human breast milk analysis. The sample pretreatment and chromatographic separation conditions have been optimized, and the method has been validated. Comparing with the conventional liquid-liquid extraction (LLE)-HPLC separation, proposed SPE-C30 column HPLC has a higher recovery, accuracy and the degree of anti-interference capability. Those results of carotenoids contribute to the evaluation of carotenoids level in human beings. |
