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Shape like \food, daily necessities, medicine, chemical industry and agriculture in many areas by the majority of the attention of scientists. β-cyclodextrin as is currently the largest industrial production of cyclodextrin, with good nature, relatively low prices are increasingly subject to a wide range of applications and development. However, the parent β-cyclodextrin molecule itself as a body model in specific applications, there are certain limitations, such as β-cyclodextrin in the spectrum of UV, fluorescence, etc. is inert, the lack of the electron transfer, the photochromic the functional groups, it is difficult with the necessary optical instrument to study its interaction with the guest molecule, etc.: Alternatively, the parent β-cyclodextrin lack of effective function on the point in the proteasome, to increase its molecular simulation identification (Pattern Recognization , PR) capacity, so as to have the enzyme function, but also need to introduce a certain functional groups on the cyclodextrin molecule modified to become functional β-cyclodextrin derivatives; Furthermore, β-cyclodextrin molecule in water solubility of smaller, is also subject to certain restrictions on its applicability. It is necessary to appropriately chemically modified β-cyclodextrin to obtain the performance model of the main function of the β-cyclodextrin and to expand its field of application. This thesis consists of five parts, as follows: 1. Oligomeric lactic acid-modified β-cyclodextrin derivatives synthesis and its applications in drug composite and capillary electrophoresis polylactic acid (PLA) for its possess good biocompatible and biodegradable, relevant research as a drug delivery carrier has become a hot spot, if the polylactic acid groups and the functional molecular cyclodextrin bonded together, it is possible to use the characteristics of polylactic acid material, an important value medicinal materials, novel biocompatible cyclodextrin derivatives. This article using lactide (dimer of lactic acid) by ring-opening polymerization reaction, the oligomeric lactic acid group modified in the β-cyclodextrin to obtain good water-soluble, biodegradable oligomeric lactic acid base-β-cyclodextrin fine series derivatives :6-O-oligomeric lactic acid group-of β-cyclodextrin (6-oligo (D, L-lactic acid)-β-Cyclodextrin ,6-OLA-β-CD) ,6-O-Low poly (D-lactic acid) yl-β-cyclodextrin (6-oligo (D-lactic acid)-β-Cyclodextrin ,6-ODLA-β-CD) ,6-O-oligo (L-lactic) yl - β-cyclodextrin (6-oligo (L-lactic acid)-β-Cyclodextrin ,6-OLLA-β-CD), the oligomeric lactic - 2 - hydroxypropyl-β-cyclodextrin (Oligo (lactic acid) -2-hydroxypropyl-β-Cyclodextrin, OLA-2-HP-β-CD), the oligomeric lactic -2 - hydroxyethyl-β-cyclodextrin (oligo (lactic acid)-2-hydroxyethyl-beta-Cyclodextrin OLA-2-HE-β-CD). Oligomeric lactic acid base-β-cyclodextrin aqueous solution in the stability studies, found that the modified polylactic acid side chain can be degraded, dynamic degradation controlled release mode is proposed for the first time on this basis, the traditional cyclodextrin release drug polylactic acid spraying organic combination drug amoxicillin, controlled release of simvastatin, lovastatin. Poly lactic acid side chain degradation of find the oligomeric lactic yl-β-cyclodextrin in the dynamic degradation control the release pattern can be a significant impact (clathrate stability constant from 2.4 × 10 the clathrate spraying of amoxicillin < sup> 5 dropped 137.3M -1 ). By DSC, FTIR 1 HNMR reasons for controlled release generating dynamic degradation Discussion that polylactic acid side chain provides a force like a hydrogen bond with the guest molecules, thus increasing the oligomerization capability of lactic acid base-β-cyclodextrin. The 6-O-oligomeric lactic acid base-β-cyclodextrin, of the oligomeric lactic -2 - hydroxypropyl-β-cyclodextrin on drug solubilization and stability experiments, found that the 6-O-oligomeric lactic acid yl-β-cyclodextrin can be effectively solubilized and stabilized of amoxicillin, simvastatin, lovastatin. Oligomeric lactic acid 2 - hydroxypropyl-β-cyclodextrin can effectively stabilize ozagrel. And using the phase-solubility method for the determination of 6-O-oligomeric lactic acid base-β-cyclodextrin (MW = 1637) and α-naphthaleneacetic acid inclusion ratio of 1:1, and the binding constant of K = 177.67M -1 . 6-O-oligomeric lactic acid-based-β-cyclodextrin as a chiral selector in capillary electrophoresis used to split chlorpheniramine, propranolol, ketone ketotifen three kinds of drugs. Of Ketotifen The Fen split reached very good results ,6-O-oligomeric lactic acid base-β-cyclodextrin (mw = 1637)-β-reached Rs = 6.5,6-O-oligomeric lactic acid-based cyclodextrin (MW = 1307) reached Rs = 3.2. And found that the high molecular weight 6-O-oligomeric lactic acid base-β-cyclodextrin with respect to low molecular weight 6-O-oligomeric lactic acid group-of β-cyclodextrin have a better split. And speculated that the polylactic acid group may occur with the N atom of the chiral drug role. Derivatives and their thermal stability 2.β-cyclodextrin esters in many cyclodextrin derivatives, ester derivatives play an important role. Cyclodextrin having a cavity of this unique structure, with respect to an ordinary ester compound, and may generate additional tension on the ester bond Since cavity clathrate thus, have an impact on its stability. Cyclodextrin itself can simulate ester hydrolase, is also likely to impact their own ester bond, there is no research specifically true cyclodextrin ester bond stability. We synthesized a variety of novel cyclodextrin ester derivatives :6-O-single methyl maleate acyl-β-cyclodextrin, 2-O-(4 - hydroxybutyrate acid)-β-cyclodextrin, ethylene amine-tetra-acetic acid-β-cyclodextrin, nitrilotriacetic ,6-O-triacetic acid-β-cyclodextrin Laid-pivaloyl-beta-cyclodextrin ,6-O-xanthan-beta-cyclodextrin, 6 ,6-O-hexadecyl alcohol phosphorus acid-β-cyclodextrin ,6-O,-O-β-cyclodextrin-dodecanol phosphoryloxymethyl ,6-O-tetradecyl alcohol phosphoryloxymethyl-beta-cyclodextrin. - octadecanol phosphoryl-β-cyclodextrin. By DSC / TGA 6-O-single-methyl maleic acid acyl-β-cyclodextrin, 2-o-(4 - hydroxybutyrate)-beta-cyclodextrin, ethylenediamine tetra-acetic acid-of β-cyclodextrin fine, nitrilotriacetic ,6-O-triacetic acid-β-cyclodextrin Laid-pivaloyl-beta-cyclodextrin ,6-O-xanthan-β-cyclodextrin ,6-O-dodecyl alcohol phosphoryloxymethyl -β-cyclodextrin ,6-O-tetradecyl alcohol phosphoryloxymethyl-beta-cyclodextrin ,6-O-octadecyl alcohol phosphoryloxymethyl-β ,6-O-hexadecyl alcohol phosphoryloxymethyl-β-cyclodextrin - cyclodextrin ,6-Ola-beta-cyclodextrin, OLA-HP-β-cyclodextrin, 6 - oligo (L-lactic acid), the base-β-cyclodextrin ,3-O-benzoyl - analysis of the thermal stability of β-cyclodextrin and 6-O-benzoyl-β-cyclodextrin. DSC / TGA analysis showed that the 3-O-benzoyl-β-cyclodextrin and the 6-O-benzoyl-beta-cyclodextrin, the modified location of the different substituents will lead to different thermal stability, DSC / TGA curve of 3-O-benzoyl-beta-cyclodextrin in 176 ℃ began weightlessness, 6-O-benzoyl-β-cyclodextrin is 274 ° C. 3 new thermal stimulation response based on the reversible Diels-Alder reaction crowned the synthesis and applications of cyclodextrins crown the presence of cyclodextrin supramolecular systems is of great significance. Crown introduction can give whole molecule brings different hydrophilic or lipophilic region, can improve the solubility of the cyclodextrin in the particular solvent; the presence of the crown also limits the clathrate molecular rotational freedom, can change cyclodextrin fine for the inclusion of specific molecules capacity;, crown and metal ion complexation, as metalloenzymes simulation or phosphorus, nitrogen ligand catalytic active center. In this paper, the anhydride aminolysis reaction, the reversible Diels-Alder reaction groups introduced the cyclodextrin crown group, providing a new controllable cyclodextrin inclusion system. Ethylenediamine-β-cyclodextrin and furan / maleic anhydride cycloaddition product and anthracene / maleic anhydride adducts reaction two new crowned cyclodextrin derivatives. Found on the product DSC / TGA test, anthracene / maleic anhydride adducts crowned β-cyclodextrin 135-191 ℃ anthracene structure off. And further found that the anthracene structure stripped interested benzoic clathrate impact. 4. Synthesis of a new class of dendritic cyclodextrin derivatives with microspheres of drug-loaded applications an easy way through the semi-solid state reaction dendritic-cyclodextrin derivatives, this new derivative Since cyclodextrin tapered cavities and long dendritic functional group. Synthetic derivatives to achieve a micro-emulsion - solvent evaporation method spheroidizing. The microspheres of products I 2 static loss experiments, the dendrimer peripheral modification can significantly slow down the clathrate I 2 molecules release by the ratio of the length of the chain change to achieve different release rate. Wherein, when the raw material octadecanol: ethanol = 1:1, I 2 release the slowest, and only under the same conditions of β-CD, one of the 250 points. Catalysis in Organic Synthesis cyclodextrin 5.β-cyclodextrin cavity interactions, and the hydrophobic organic molecules form a reversible main - guest complex, to improve the solubility of the hydrophobic guest molecules in water, so that The organic reaction may be in the water of the environment-friendly. Meanwhile, the cavity is rich in electrical properties, it is possible to affect the electrical environment of the guest molecule, the reaction can be effectively carried out under mild conditions. Hydroxyl groups on the cyclodextrin cone by hydrogen bonds between the subject and object of the reaction toward the favorable direction. Use the the cyclodextrin derivatives catalytic H 2 O 2 epoxidation of styrene, found that the catalytic effect of the order of carboxymethyl-β-cyclodextrin> high degree of substitution β-cyclodextrin sulfonate> Low-substituted degree of the sulfonic acid ester of β-cyclodextrin> β-cyclodextrin, sulfuric acid, acetic acid. Proves with carboxyl functional groups of β-cyclodextrin as the one hand, can be used as a phase transfer catalyst, on the other hand can be used as a reaction catalyst, the catalytic effect to separate the cyclodextrin, separate sulfuric acid, acetic acid. The use of cyclodextrin catalytic acetylacetonate oximation reaction without use of sulfuric acid at high temperatures to achieve acetylacetone oximation. Cyclodextrin catalyzed oximation with traditional acetylacetonate compared to the catalytic mechanism of the two may be different, the catalysis is to play with the guest molecule selective complex action \role, in addition of β-CD \selectivity increases, effective to suppress side reactions. Use cyclodextrin and KI aqueous phase at room temperature to achieve the addition reaction of acrylonitrile with water. Cyclodextrin introduction of one hand as a phase transfer catalyst to improve the the hydrophobic acrylonitrile a solubility in water, while the hydroxy group of the β-CD cavity surrounding also be involved in the activation of the reaction. The main innovations of the paper is as follows: (1) for the first time to the design and synthesis of a water-soluble good, biodegradable new oligomeric lactic acid modified β-cyclodextrin derivatives :6-OLA-β-CD (mw = 1236 , n = 0.8, x = 1.7) ,6-OLA-β-CD (mw = 1339, n = 1.219, x = 2.325) ,6-OLA-β-CD (mw = 1469, n = 1.68, x = 2.76 ) ,6-OLA-β-CD (mw = 1637, n = 1.55, x = 4.48) ,6-ODLA-β-CD (mw = 1297) ,6-OLLA-β-CD (mw = 1309), OLA -HP-β-CD (x = 1.4), OLA-HP-β-CD (x = 10.3), OLA-HE-β-CD. (2) first proposed the dynamic degradation controlled release model, the traditional cyclodextrins release polylactic acid application method combined to achieve a drug amoxicillin, simvastatin, lovastatin controlled release . Found that the polylactic acid in the degradation of the side chain of the the oligomeric lactic yl-β-cyclodextrin, on the the amoxicillin package together a significant impact. ,6-O-oligomeric lactic acid base-β-cyclodextrin, of the oligomeric lactic -2 - hydroxypropyl-β-cyclodextrin on drug solubilization and the stability of the experiment and found that 6-O-Low The polylactic acid-base-β-cyclodextrin can be effectively solubilized and stabilized of amoxicillin, simvastatin, lovastatin. Oligomeric lactic acid 2 - hydroxypropyl-β-cyclodextrin can effectively stabilize ozagrel. (3) for the first time in the 6-O-oligomeric lactic acid-based-β-cyclodextrin in capillary electrophoresis as a chiral selector for split chlorpheniramine, propranolol, ketone ketotifen three kinds of drugs. Ketotifen The Fen split reached very good results. And found that the high molecular weight 6-O-oligomeric lactic acid base-β-cyclodextrin with respect to low molecular weight 6-O-oligomeric lactic acid group-of β-cyclodextrin have a better split. (4) Synthesis of ester derivatives of a variety of novel cyclodextrin :6-O-mono-methyl maleic acid acyl-β-cyclodextrin, 2-O-(4 - hydroxybutyrate)-beta-cyclodextrin, B diamine tetra acetic acid-β-cyclodextrin, nitrilotriacetic acid-β-cyclodextrin ,6-O-Laid-pivaloyl-β-cyclodextrin ,6-O-xanthan-β-cyclodextrin, 6-O-dodecyl alcohol phosphate acyl-β-cyclodextrin ,6-O-tetradecyl alcohol phosphoryloxymethyl-beta-cyclodextrin ,6-O-hexadecyl alcohol phosphoryloxymethyl-beta-cyclodextrin, 6 - O-octadecyl alcohol phosphoryloxymethyl-β-cyclodextrin. (5) by DSC / TGA analysis of the thermal stability of a variety of novel cyclodextrin ester derivative. First found in 3-O-benzoyl-beta-cyclodextrin and 6-O-benzoyl-beta-cyclodextrin, the modified location of the different causes DSC / TGA different substituent. 3-O-benzoyl-beta-cyclodextrin in 176 ℃ began weightlessness, while the 6-O-benzoyl-β-cyclodextrin is 274 ° C. (6) Synthesis of two new thermal stimulation response to crowning cyclodextrin derivatives: 7 - oxabicyclo [2.2.1] hept-5 - ene-2 ??,3 - the dicarboxylic acid Crownplus cyclodextrin, anthracene / Ma acid adducts Crownplus cyclodextrin. DSC / TGA confirmed that part of the crown crowned cyclodextrin can be off by heating. Crowned cyclodextrin thermal stimuli-responsive molecular recognition of benzoic acid. (7) in an easy way through the semi-solid phase was synthesized by the reaction of class dendrimers cyclodextrin derivative, and this new derivatives having the conical cavity of the cyclodextrin and long dendritic functional group. The of I 2 static loss experiments, the dendrimer peripheral modification can significantly slow down the clathrate I 2 molecules release, and can be achieved through changes in the ratio of the length of the chain of different release rate. Wherein when octadecanol: ethanol = 1:1, I 2 release the slowest, and only under the same conditions of β-CD, one of the 250 points. (8) Use the a cyclodextrin catalytic H 2 O 2 epoxidation of styrene, found that the catalytic effect of order carboxymethyl-β-cyclodextrin substituted β> High - cyclodextrin sulfonate> Low-substituted β-cyclodextrin sulfonate> β-cyclodextrin, sulfuric acid, acetic acid. Prove with carboxymethyl, β-cyclodextrin of the sulfonic acid functional groups of the one hand, can be used as a phase transfer catalyst, the other hand can be used as a reaction catalyst, the catalytic effect is good in a separate cyclodextrin, separate sulfuric acid, acetic acid . (9) The use of cyclodextrin catalytic acetylacetonate oximation reaction, without the use of sulfuric acid, higher temperatures to achieve the oximation reaction of the acetylacetone. (10) use of cyclodextrin and KI in the ambient temperature water phase to achieve the addition reaction of water to acrylonitrile.
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