ABSTRACT
BACKGROUND: Cyclodextrins selectively bind with reactants and facilitate chemical reactions through supramolecular catalysis, similar to the mechanisms employed by enzymes. In this paper, ß-cyclodextrin was used as a supramolecular catalyst in water as a green, reusable, and ecofriendly solvent system to synthesize spiro-benzimidazoquinazolinones and spiro-benzothiazoloquinazolinones. OBJECTIVE: A supramolecular catalyst ß-cyclodextrin (ß-CD) is used to synthesize spiro- benzimidazoquinazolinones and spiro-benzothiazoloquinazolinones via multicomponent reaction involving the condensation of dimedone, isatin, and 2-aminobenzimidazole/2-aminobenzothiazole. METHODS: In a 50 mL round bottom flask were added the respective mixture of substituted isatin (1 mmol), dimedone (1mmol), and 2-aminobenzimidazole/2-aminobenzothiazole (1 mmol) in water (5ml) containing ß-CD (113 mg, 10 mol. %) was stirred at 60oC for 30 min. The desired product was obtained with excellent yield. After completion of the reaction (monitored by TLC), the reaction mixture was quenched with water and extracted with ethyl acetate (4X5ml). The combined organic layers were washed with brine solution, dried over anhydrous Na2SO4 and evaporated under reduced pressure. The crude product was purified by silica gel chromatography. RESULTS: ß-cyclodextrin catalyst showed very good efficiency in the synthesis of the desired compounds and can be easily recovered and reused at least five times with minimal deactivation in catalytic activity. CONCLUSION: The catalyst demonstrated remarkable effectiveness in producing the target compounds and conducting the reaction with different initial substances, resulting in excellent yields of the products, thereby confirming the broad applicability and versatility of this method.
ABSTRACT
Lycium (also known as Goji berry) is used in traditional Chinese medicine (TCM) with claimed benefits, including eye and liver protection, immune system fortification and blood glucose control. The commercially available product comes from either the L. barbarum or L. chinense species, with the former dominating the marketplace due to its better taste profile. The main objective of this study was to develop a validated LC-ESI-MS/MS method to quantify multiple key bio-active analytes in commercially available Lycium berries and to qualitatively assess these samples using a principal component analysis (PCA). A LC-ESI-MS/MS method for the quantitation of seven analytes selected using the Herbal Chemical Marker Ranking System (Herb MaRS) was developed. The Herb MaRS ranking system considered bioavailability, bioactivity and physiological action of each target analyte, its intended use and the commercial availability of an analytical standard. After method optimization combining high resolving power with selective detection, seven analytes were quantified and the Lycium samples were quantitatively profiled. Chromatographic spectra were also obtained using longer run-time LC-UV and GC-MS methods in order to qualitatively assess the samples using a principal component analysis (PCA). The result of the method validation procedure was a 15.5 min LC-ESI-MS/MS method developed for the quantification of seven analytes in commercial Lycium samples. Wide variation in analyte concentration was observed with the following results (analyte range in mg/g): rutin, 16.1-49.2; narcissin, 0.37-1.65; nictoflorin, 0.26-0.78; coumaric acid, 6.84-12.2; scopoletin, 0.33-2.61; caffeic acid, 0.08-0.32; chlorogenic acid, 1.1-9.12. The quantitative results for the L. barbarum and L. chinense species samples indicate that they cannot be differentiated based on the bio-actives tested. A qualitative assessment using PCA generated from un-targeted LC-UV and GC-MS phytochemical spectra led to the same conclusion. The un-targeted quantitative and qualitative phytochemical profiling indicates that commercial L. barbarum and L. chinense cannot be distinguished using chemical analytical methods. Genetic fingerprinting and pharmacological testing may be needed to ensure the efficacy of commercial Lycium in order to validate label claims.
